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Trihydrocarbyltin complexes of transitional metal cyanides
359
Jo&l of Orgmmnt&kz CkmWy, @ Ekewier Seqtmia Sk, Lamann e -
TRIHYDROCARRYLTIN CYANIDES
R. USON,
J. FORNIES,
i85 (1980) 359-366 Printed in The Netherlands
COMPLEXES OF TRANSI’I’ION METAL
M.A. USON and E. LALINDE
Department of Inorganic Chemistry,
University of Zaragoza (Spain)
(Received July 17th, 1979)
Cationic single-bridged trinuclear cyan0 complexes are obtained by treating trihydrocarbyltin perchlorate (SnR,O,ClO,) (R = alkyl or aryl) with neutral transition metal monocyanides, whereas treatment with the corresponding neutral or anionic transition metal polycyanides gives neutral single-bridged polymeric cyan0 compounds. In every case the tin atoms are pentacoordinated with the three R groups in the equatorial and two CN groups (or, respectively one CN and one OClO, group) in the axial position of a trigonal bipyramid.
Introduction
The synthesis of covalent per&lo&o derivatives from-the corresponding halo complexes, according to eq. 1 and the subsequent substitution of the perchlorato L,.,MX f AgC104 + A@
f L,MOC103
(1)
group, (which has a low coordinating capacity) by neutral (eq_ 2) or anionic ligands (eq_ 3) has frequently been used by us [l] and by others [2] for the L,MOC103 + L’ 4 [L,ML’]ClO,
(2)
LnMOC103
(3)
f M’X
+ M’C104
-I- L&IX
preparation of neutral and anionic organometalhc domplexes of gold [la-lc], nickel [2a-2c], palladium [ld-lg,2d], platinum [lh-lj] and rhodium [lk-111. If reaction 1 is +mried oukin a non-donor solvent under anhydrous conditions the intermediate perchlorato complex can sometimes be isolated, but is frequently unstable. Even so, after removal of the precipitated silver halide, the filtrate can in every case be used for &ocesses 2 and 3. Mainly because of the solubihty of L,MX it is, however, sometimes necessary to work in another type of solvent. In these cases it seems appropriate to employ
360
acetone, wbich,.though it displaces the perchiorato group giving a (sometimes isolable) cationic perchlorate (eq. 4), can afterwards readily be displaced by L&X
+ AgClO, =
AgX f [L,M(Me&O),
]ClO,
(4)
reactions of type 2 or 3. We consider below the reaction of solutions of perchloratotrialkyltin or perchloratotriaryltin compounds with several cyano complexes of transition metals. These behave as a ligand L’ (eq. 2) since their cyan0 group still has a potentially N-donor atom which causes.the displacement of the perchlorato group or the acetone. The process allows the preparation of polymeric (finite or ismite) complexes with the cyan0 group bridging the tin and the transition metal
atoms.
Some of these results were the subject of a preliminary communication 131.
Results and discussion The precursor solutions used in the present study were prepared by treating the organocblorocomplexes SnR&X (R being Me, Bu or Ph) with benzene or acetone solutions of AgC1G4, and removal of the AgCl. As reported ]4] for the methyl complex [SnMe302C102], in the solid state the pentacoordinated tin atoms are bridged by the perchlorato ligands.
Tbis bridging system is cleaved in methanol to give the pentacoordinated cationic perchlorate [SnR&]C104 (S = solvent). Thus, whilst our benzene solutions are likely to contain [Sn(O&lOz)R,], the acetone solutions are assumed to contain [SnR3(Me,C0)&X0,, but the reaction products with cyano-transition metal
complexes
-are in each case the same.
(a) Reactions with monocyanides 2
Po’(CN)(C6F,)(PPh&
+
PPh:,
R
r
I C6F5 -Pd-CN
1
Sn-NC-Pd-
A
I
R
R3] PPh3
I
-
PPh3
[Srdo,ClO,)
R
(I,R
=
Me;
m,R
=
Ph)
I CIO,
c6F5
I PPh,
1
(51
361
Thereaction(1/2)ofbenzene oracetonesolutionsofperchlo~totrihydrocarbyltin Sn(0&102)R3 with cyanopenkfluorophenylbis(triphenylphosphine)pallad.ium(II) [Pd(CN)(C,F,)(PPh,),] gives cationic trinuclear complexes (see eq. 5). The complexes I and ‘iII are precipitated instantaneously whatever theusedmolarratioofthereagentsusedbutthebu~lcomplex(II)canonly
be obtained by use of a 2/l mole ratio as in eq. 5. A l/l
mole ratic leads to the PPh3
Pd(CN)(CgF5)(PPh3)2
+
~n102C102)R3]
-
I
i O$O-Sn-NC-Pd-C,F, /\ R.
(6) I PPh,
R
(El
R
=
Bul
precipitation of the neutral complex IV, (see eq. 6), which contains a monodentate (C,,) perchlorato group (see below). The tendency of tin to adopt a coordination number of 5 means that the reaction of Sn(OzC102)R3 with di- or poly-cyano-transition metal complexes leads to polymeric end products_ Thus the reaction with neutral polycyano complexes yields cationic polymers, whereas anionic polycyanides give neutral polymers_ (b) Reactions with di- and poly-cyanides The reaction with trar&4icyanobis(triphenylphosphine)palladium(II),
according to eq. 7 gives rise to the immediate precipitation of the cationic 7
(Y)
polynuclear complex V. The reactions with other cationic dicyano complexes, such as (Bu,N) ]Ag(CN)J or K]Au(CN),] (which are very little soluble in benzene require the use of acetone (Me&O = S) as reaction medium) also give neutral complexes (eq. 8). R Q[M(CN),]
+ [SnR&]C104
+ &Cl04 + 2 S + t R’
Sn
x
(8)
f
(VI, M = Ag, Q = B&N, R = Me; VII,M=Ag,Q=R&N,R=Ph; VIII,M=Au,Q=K,R=Me; IX,M=Au,Q=K,R=Bu; X,M=Au,Q=K,R=Ph) The complexes separate out upon mixing the two solutioijs. The simuh~eously
362
precipitated QClO, can be removed by washing with water. No reaction could be observed for M = Ag and R = Bu. Complex V is decomposed by an acetone solution-of NaBPb finally giving trans-Pd(CN)2(PPh3)2. Treatment with tetra- and hexa-cyanometallates gives immediate precipitation of the corresponding neutral polymers. K2[M(CN)J
+ 2 [SnR3S$104
+ 2 KCIOa + 4 S + {(R3Sn)2[(y-CN),]},
(9)
(XI,W=Pd,R=Me; XII,M=Pd,R=Bu; XIII, M = Pd, R = Ph; XIV,M=Pt,R=Me; XV,M=Pt,R=Bu; XVI,M=Pt,R=Ph) In the light of the square planar coordination of Pd or Pt, these polymers can be expected to have an infinite twodimensional structure (Fig. 1). When K3[Fe(CN)6j is used no reaction occurs for R = Me, whereas when R = Bu or Ph it gives neutral polymeric complexes (eq. lo), which are assumed to K3 [Fe(CN)6] + 3 [SnR3S2]C104-+ 3 KC104 f 6 S + { [R,Sn],[(y-CN),Fe]]z
(10)
have a threedimensional structure. (c)
Solu bility and conductivity
expected for macromolecular substances, all the polymeric complexes (V-XVIII) are insoluble in water and organic solvents. The bi- and t&nuclear complexes (I-IV) are soluble k chloroform, dichloromethane and nitromethane, and complexes II-IV are also soluble in acetone. All are insoluble in n-hexane As
fig.
1. Ropoeed
structure
of the {[R$~xI~C(~-NC)&%I~
complexes.
(M = Pd or Pt; R = Me. Bu. Ph).
363
and benzene. The conductivities of the soluble complexes show [5] that they behave as l/1 electrolytes, in accordance with the proposed formulae. (d) IR spectra The discussion above requires that the reaction pri;ducts contain only bridging CN groups while the starting materials contain only terminal CN groups. In accordance with this, the v(CN) stretching vibration of the resulting complexes is always shifted towards higher energy, and only a single band is observed [Sl. Table 1 shows the values of Au (Au = v(CN),.,~~~~- V(CN)te-inal) for all the new complexes. AU the pentafluorophenyl derivatives exhibit absorption at -15OOvs, 105Os,
950vs and 800s cm-’ due to the CsFS ligand [7] along with those of the two mutually tians-PPh, groups [S] at 525s, 515s and 502s cm-’ (complexes I-IV). All the methyl derivatives show a strong absorption at 569-555 cm-’ assignable to the v,(Sn--C) stretching mode, and only complex XIV also shows a very weak band at 505 cm-’ assignable to v,,(Sn-C)_ This is in good agreement with the proposed trigonal bipyramidal structure, with the three methyl groups in equatorial position and the two cyan0 groups at axial sites. This agrees with the structure proposed
for other trimethyl
derivatives of SnR,X,
with X being
a bridging ligand (X = F [9]; Cl, Br [lo]; Cl04 14,111; BF4 [12], AsF6, SbF6 [13]; RCOO [14] or alkyl- and aryl-imidazole [15]). The corresponding absorptions for the butyl derivatives located in the 650-600 cm-’ region, which are always weak [16] are in our complexes masked by bands due to the PPh3, CIO, or CN group. Our phenyl derivatives show ttio medium bands at 280-270 and 240-230 cm-‘, assignable to symmetric and assymetricv(Sn-C) [17], showing that the Sn-C bonds are not coplanar. Finally, all the ionic complexes (I, II, III and V) show absorptions at 1100s and 630m cm’-’ assignable, respectively, to v3 or v4 vibrations of the perchlorato group (Td). In complex IV the bands expected at 1100 and 630 cm-’ are split, and are located, respectively, at 1140 and 1040 cm-’ and at 615 and 625 cm-‘, corresponding to the vl, v4 and v3, us vibrations of the 0C103 group (C,,). This complex shows another band (A,) at 915 cm-* assignable to v(Cl--0), which would be IR active for C3” symmetry, and this confirms the formulation proposed for this compound [18]. Experimental C, H and N analyses were carried out with a Perkin-Elmer 240 -microanalyzer. Melting points were measured on a Buchi apparatus (model Dr. Tottoli) and are uncorrected.
Conductivities
were determined
in approximately
5 X lo4
M solu-
tions with a Philips PW 9501/01 conductimeter. IR spectra were recorded (over the range 4000-200 cm-‘) on a Perkin-Elmer 599 spectrophotometer using Nujol mulls between polyethylene plates_ Pd(CN)(C,F,)(PPh 3) 2 was prepared as described elsewhere.1191. Pd(CN)*(PPh& was obtained by treating a solution of Pd12(PPh3)2(9.01 g, 10 mmol) in 260 ml of acetone with freshly prepared AgCN (2.60 g, 20 mmol) for 60 min at room temperature with exclusion of light. The AgI was filtered off and
(Q4.44) 69.11 (69.39) 17.91 (18,bS) 47.02 (47.11) 14.65 (14.65) 31.38 (31.19) 40.69 (40.10) 22.36 (22.32) 42.30 (42.64) 62.75 (62.77) 19.74 (19.26) 38.78 (38.26) 4&62 (48.08) 46&l (46.22) 66.46 (67.11)
3.59 (3.69)
(2,80) 2.92 (2.96) 2.14 (2.20) 5.03 (6.06) 2.65 (2. G2) 3.26 (3.27) 6.09 (6.89) 2.36 (3.32) 2.90 (2.09) 6.27 (6.19) 3.21 (3.03) 7.07 (7.65)
(4:73) 4.04 (4su) 2,69
3.76 (3.64) 4.31 (4.30) 3.60 (3.00) 4 P,F.
64.75 (66,93) 67.62 (67.77) 68.59
(69.55) 7.d .-._-AC
11
d
Foun: (calcd.) % _.-
AND OTHER DATA FOR POLY NUCLEAR COMPLEXES --_-
a In nltromcthnno. b In ocotono, c Inoolublo.
Complex
ANALYTICAL
TABLE 1
((6179) 6,09 (6.20) 4.82 (4.68) 10.24 (10.41) 6,96 (7.09) 6,77 (6,lb) 9.26 (8.94) 6.06 (6.37) 4.76 (6.61) 7.78 (7.77) 7.16 (6.66)
1.46 (1.47) 1,41 (1.37) 1.35 (1.34) 1.16 (1.16) 2.69 (2.47) 8.68 (8.65) 6.13 (6.49) 6.74
N
-
----
c
13Clb
287 (dec.) 210 (dec.)
182 (dec,) 163 (dac,)
29 29 29 32 27 21 28 22
2166 2166 2166 2166 2160 2100 2146 2140
>300
>a00
>300
243 (dco.)
r
220 (deo.) 26
2170
266 (dec. )
216 (dcc.) 26
26
2171
>300
263
192 (dot,)
203 (do&)
179 (dot,)
2170
20
26
2166 2160
30
2b
26
2160
2165
2166
195 (dcc,)
25
2166
112 b 62.9 a
lSB(doc.)
M& (“C)
47
AV (cm’*)
2177
WW complex (cm-l)
116 b
AM (ohm-l cm2 mol+)
365
Depending cm their subsequentuse these complexes were preparedeitherin benzeneor ~&XXX?by tseatingstuichiometricamonntsof the urgauutincomplex &R&I. with Al;cro, for 30 miu at room ~mp~rat~e. After ~&xMw&~ of the AgCl the filtratewas used for furtheEzeacticmswithout additions& fxe&merit.
To a s&&ion of Sn(O&lO$?h~ (0.5 mmol) in 25 ml of benzenewas klded Pd(CN)2(PPh3)2(0.3415 g, 0.5 mmol) in 40 ml of dicbloromethane.The microcrystaBineprecipitate,which was difficult to Elter of& was separatedby ~eu~~gatio~ and w_+hedwith hexane (70% yield)+
To a so&A&m of Q~~~~~~~ @I =+Ag, Q = ByN; M = Au, Q = K) (1 mmol) in 25 ml of acetonewas added an equimolecniarsolution of Sn(0&10.&3, in 25 mI of acetone, The immedi&eIy precipitatedwhite (or in the case of VIII y~~o~h) solid was filtered off and repeatedlywmhed with wa~r~ac~toue (yieids: complex VI, 63%; WI, 7643a;VE& 66% $X, 64%; X, 81%).
To a solution of I&[M(CN).J (1 mmol) in 10 ml of I&O and 15 ml of acetone was added a solution of Sn(O&lO,)& (2 rnmol) in acetcme(l/2 mole ratio).. Stirringwas continuedfor 3HO mb. The wZ&x.precipitatewas filtered off and washedwith benzeneor acet?ton.e and then with hexane (yields: complex XI, 81% XII, 88@&XIII, 85%; XIV, 91% xv, 81%; XVI, 93%).
366
{[R&z],[(p-NC)&e& (XVII, R = Bu; XVIII, R =Ih) The reaction was carried out as before by treating 1 mm01 of the iron com-
(vii)
plex with 3 mmol of the organotin perchlorato.complex. The resulting pounds were washed with acetone (yields; XVII, 95%; XVDI, 96%).
com-
References P. Royo. A. Laguna and J. Garcia. Rev. Acad. Cienaias Zaragoza. 28 (1973) 67;
1955. Sot..
(1963)
85; @)
H.C. Cla&
H. Kriegsmann and S. Pischtschan. 2. Anorg. AUg. Chem.. 308 (1961) 2l2. R. Okawxa, B-J. Hathaway and D.E. Webster, Proc. C&m. Sot.. (1963) 13. B-J. Hathaway and D-E. Webster. Rec. Chem. Sot.. (1963) 14. HX. Clark and R.J. O’Brien. Inorg. Chem.. 2 (1963) 1020. (a) R. Oka-. D.E. Webster gnd E.G. Rochow. J. Amer. Chem. Sot.. 82 <1960) 3278; Okawara and M. Oham, J. OrganometaL Chem.. 1 (1964) 360. R. Gassend. J.C. Maire and J.C. Pommier. J. OrganometaL Chem-. 132 (1977) 69. J. Madelshon. A. Marchand and J. V&de. J. OrganometaL Chem.. 6 (2.966) 25. R.C. Poller. Spectrochim. Acta. 22 (1966) 935. B.J. Hathaway and A.E. Underbill. Chem_ Sot.. (1961) 3091. R. Usdn, P. Royo and J. Forx&s, Rev. Acad. Ciencias. Zaragoza. 28 (1973) 349. J-H_ Bigelow. Inorganic Synth.. 2 (1946) 245. G. Brauer. Qufmica Inorganica heparativa, Ed. Reverti, Barcelona. 1958. P. 630.949.
R-J-
(b)
R.
Jo&l of Orgmmnt&kz CkmWy, @ Ekewier Seqtmia Sk, Lamann e -
TRIHYDROCARRYLTIN CYANIDES
R. USON,
J. FORNIES,
i85 (1980) 359-366 Printed in The Netherlands
COMPLEXES OF TRANSI’I’ION METAL
M.A. USON and E. LALINDE
Department of Inorganic Chemistry,
University of Zaragoza (Spain)
(Received July 17th, 1979)
Cationic single-bridged trinuclear cyan0 complexes are obtained by treating trihydrocarbyltin perchlorate (SnR,O,ClO,) (R = alkyl or aryl) with neutral transition metal monocyanides, whereas treatment with the corresponding neutral or anionic transition metal polycyanides gives neutral single-bridged polymeric cyan0 compounds. In every case the tin atoms are pentacoordinated with the three R groups in the equatorial and two CN groups (or, respectively one CN and one OClO, group) in the axial position of a trigonal bipyramid.
Introduction
The synthesis of covalent per&lo&o derivatives from-the corresponding halo complexes, according to eq. 1 and the subsequent substitution of the perchlorato L,.,MX f AgC104 + A@
f L,MOC103
(1)
group, (which has a low coordinating capacity) by neutral (eq_ 2) or anionic ligands (eq_ 3) has frequently been used by us [l] and by others [2] for the L,MOC103 + L’ 4 [L,ML’]ClO,
(2)
LnMOC103
(3)
f M’X
+ M’C104
-I- L&IX
preparation of neutral and anionic organometalhc domplexes of gold [la-lc], nickel [2a-2c], palladium [ld-lg,2d], platinum [lh-lj] and rhodium [lk-111. If reaction 1 is +mried oukin a non-donor solvent under anhydrous conditions the intermediate perchlorato complex can sometimes be isolated, but is frequently unstable. Even so, after removal of the precipitated silver halide, the filtrate can in every case be used for &ocesses 2 and 3. Mainly because of the solubihty of L,MX it is, however, sometimes necessary to work in another type of solvent. In these cases it seems appropriate to employ
360
acetone, wbich,.though it displaces the perchiorato group giving a (sometimes isolable) cationic perchlorate (eq. 4), can afterwards readily be displaced by L&X
+ AgClO, =
AgX f [L,M(Me&O),
]ClO,
(4)
reactions of type 2 or 3. We consider below the reaction of solutions of perchloratotrialkyltin or perchloratotriaryltin compounds with several cyano complexes of transition metals. These behave as a ligand L’ (eq. 2) since their cyan0 group still has a potentially N-donor atom which causes.the displacement of the perchlorato group or the acetone. The process allows the preparation of polymeric (finite or ismite) complexes with the cyan0 group bridging the tin and the transition metal
atoms.
Some of these results were the subject of a preliminary communication 131.
Results and discussion The precursor solutions used in the present study were prepared by treating the organocblorocomplexes SnR&X (R being Me, Bu or Ph) with benzene or acetone solutions of AgC1G4, and removal of the AgCl. As reported ]4] for the methyl complex [SnMe302C102], in the solid state the pentacoordinated tin atoms are bridged by the perchlorato ligands.
Tbis bridging system is cleaved in methanol to give the pentacoordinated cationic perchlorate [SnR&]C104 (S = solvent). Thus, whilst our benzene solutions are likely to contain [Sn(O&lOz)R,], the acetone solutions are assumed to contain [SnR3(Me,C0)&X0,, but the reaction products with cyano-transition metal
complexes
-are in each case the same.
(a) Reactions with monocyanides 2
Po’(CN)(C6F,)(PPh&
+
PPh:,
R
r
I C6F5 -Pd-CN
1
Sn-NC-Pd-
A
I
R
R3] PPh3
I
-
PPh3
[Srdo,ClO,)
R
(I,R
=
Me;
m,R
=
Ph)
I CIO,
c6F5
I PPh,
1
(51
361
Thereaction(1/2)ofbenzene oracetonesolutionsofperchlo~totrihydrocarbyltin Sn(0&102)R3 with cyanopenkfluorophenylbis(triphenylphosphine)pallad.ium(II) [Pd(CN)(C,F,)(PPh,),] gives cationic trinuclear complexes (see eq. 5). The complexes I and ‘iII are precipitated instantaneously whatever theusedmolarratioofthereagentsusedbutthebu~lcomplex(II)canonly
be obtained by use of a 2/l mole ratio as in eq. 5. A l/l
mole ratic leads to the PPh3
Pd(CN)(CgF5)(PPh3)2
+
~n102C102)R3]
-
I
i O$O-Sn-NC-Pd-C,F, /\ R.
(6) I PPh,
R
(El
R
=
Bul
precipitation of the neutral complex IV, (see eq. 6), which contains a monodentate (C,,) perchlorato group (see below). The tendency of tin to adopt a coordination number of 5 means that the reaction of Sn(OzC102)R3 with di- or poly-cyano-transition metal complexes leads to polymeric end products_ Thus the reaction with neutral polycyano complexes yields cationic polymers, whereas anionic polycyanides give neutral polymers_ (b) Reactions with di- and poly-cyanides The reaction with trar&4icyanobis(triphenylphosphine)palladium(II),
according to eq. 7 gives rise to the immediate precipitation of the cationic 7
(Y)
polynuclear complex V. The reactions with other cationic dicyano complexes, such as (Bu,N) ]Ag(CN)J or K]Au(CN),] (which are very little soluble in benzene require the use of acetone (Me&O = S) as reaction medium) also give neutral complexes (eq. 8). R Q[M(CN),]
+ [SnR&]C104
+ &Cl04 + 2 S + t R’
Sn
x
(8)
f
(VI, M = Ag, Q = B&N, R = Me; VII,M=Ag,Q=R&N,R=Ph; VIII,M=Au,Q=K,R=Me; IX,M=Au,Q=K,R=Bu; X,M=Au,Q=K,R=Ph) The complexes separate out upon mixing the two solutioijs. The simuh~eously
362
precipitated QClO, can be removed by washing with water. No reaction could be observed for M = Ag and R = Bu. Complex V is decomposed by an acetone solution-of NaBPb finally giving trans-Pd(CN)2(PPh3)2. Treatment with tetra- and hexa-cyanometallates gives immediate precipitation of the corresponding neutral polymers. K2[M(CN)J
+ 2 [SnR3S$104
+ 2 KCIOa + 4 S + {(R3Sn)2[(y-CN),]},
(9)
(XI,W=Pd,R=Me; XII,M=Pd,R=Bu; XIII, M = Pd, R = Ph; XIV,M=Pt,R=Me; XV,M=Pt,R=Bu; XVI,M=Pt,R=Ph) In the light of the square planar coordination of Pd or Pt, these polymers can be expected to have an infinite twodimensional structure (Fig. 1). When K3[Fe(CN)6j is used no reaction occurs for R = Me, whereas when R = Bu or Ph it gives neutral polymeric complexes (eq. lo), which are assumed to K3 [Fe(CN)6] + 3 [SnR3S2]C104-+ 3 KC104 f 6 S + { [R,Sn],[(y-CN),Fe]]z
(10)
have a threedimensional structure. (c)
Solu bility and conductivity
expected for macromolecular substances, all the polymeric complexes (V-XVIII) are insoluble in water and organic solvents. The bi- and t&nuclear complexes (I-IV) are soluble k chloroform, dichloromethane and nitromethane, and complexes II-IV are also soluble in acetone. All are insoluble in n-hexane As
fig.
1. Ropoeed
structure
of the {[R$~xI~C(~-NC)&%I~
complexes.
(M = Pd or Pt; R = Me. Bu. Ph).
363
and benzene. The conductivities of the soluble complexes show [5] that they behave as l/1 electrolytes, in accordance with the proposed formulae. (d) IR spectra The discussion above requires that the reaction pri;ducts contain only bridging CN groups while the starting materials contain only terminal CN groups. In accordance with this, the v(CN) stretching vibration of the resulting complexes is always shifted towards higher energy, and only a single band is observed [Sl. Table 1 shows the values of Au (Au = v(CN),.,~~~~- V(CN)te-inal) for all the new complexes. AU the pentafluorophenyl derivatives exhibit absorption at -15OOvs, 105Os,
950vs and 800s cm-’ due to the CsFS ligand [7] along with those of the two mutually tians-PPh, groups [S] at 525s, 515s and 502s cm-’ (complexes I-IV). All the methyl derivatives show a strong absorption at 569-555 cm-’ assignable to the v,(Sn--C) stretching mode, and only complex XIV also shows a very weak band at 505 cm-’ assignable to v,,(Sn-C)_ This is in good agreement with the proposed trigonal bipyramidal structure, with the three methyl groups in equatorial position and the two cyan0 groups at axial sites. This agrees with the structure proposed
for other trimethyl
derivatives of SnR,X,
with X being
a bridging ligand (X = F [9]; Cl, Br [lo]; Cl04 14,111; BF4 [12], AsF6, SbF6 [13]; RCOO [14] or alkyl- and aryl-imidazole [15]). The corresponding absorptions for the butyl derivatives located in the 650-600 cm-’ region, which are always weak [16] are in our complexes masked by bands due to the PPh3, CIO, or CN group. Our phenyl derivatives show ttio medium bands at 280-270 and 240-230 cm-‘, assignable to symmetric and assymetricv(Sn-C) [17], showing that the Sn-C bonds are not coplanar. Finally, all the ionic complexes (I, II, III and V) show absorptions at 1100s and 630m cm’-’ assignable, respectively, to v3 or v4 vibrations of the perchlorato group (Td). In complex IV the bands expected at 1100 and 630 cm-’ are split, and are located, respectively, at 1140 and 1040 cm-’ and at 615 and 625 cm-‘, corresponding to the vl, v4 and v3, us vibrations of the 0C103 group (C,,). This complex shows another band (A,) at 915 cm-* assignable to v(Cl--0), which would be IR active for C3” symmetry, and this confirms the formulation proposed for this compound [18]. Experimental C, H and N analyses were carried out with a Perkin-Elmer 240 -microanalyzer. Melting points were measured on a Buchi apparatus (model Dr. Tottoli) and are uncorrected.
Conductivities
were determined
in approximately
5 X lo4
M solu-
tions with a Philips PW 9501/01 conductimeter. IR spectra were recorded (over the range 4000-200 cm-‘) on a Perkin-Elmer 599 spectrophotometer using Nujol mulls between polyethylene plates_ Pd(CN)(C,F,)(PPh 3) 2 was prepared as described elsewhere.1191. Pd(CN)*(PPh& was obtained by treating a solution of Pd12(PPh3)2(9.01 g, 10 mmol) in 260 ml of acetone with freshly prepared AgCN (2.60 g, 20 mmol) for 60 min at room temperature with exclusion of light. The AgI was filtered off and
(Q4.44) 69.11 (69.39) 17.91 (18,bS) 47.02 (47.11) 14.65 (14.65) 31.38 (31.19) 40.69 (40.10) 22.36 (22.32) 42.30 (42.64) 62.75 (62.77) 19.74 (19.26) 38.78 (38.26) 4&62 (48.08) 46&l (46.22) 66.46 (67.11)
3.59 (3.69)
(2,80) 2.92 (2.96) 2.14 (2.20) 5.03 (6.06) 2.65 (2. G2) 3.26 (3.27) 6.09 (6.89) 2.36 (3.32) 2.90 (2.09) 6.27 (6.19) 3.21 (3.03) 7.07 (7.65)
(4:73) 4.04 (4su) 2,69
3.76 (3.64) 4.31 (4.30) 3.60 (3.00) 4 P,F.
64.75 (66,93) 67.62 (67.77) 68.59
(69.55) 7.d .-._-AC
11
d
Foun: (calcd.) % _.-
AND OTHER DATA FOR POLY NUCLEAR COMPLEXES --_-
a In nltromcthnno. b In ocotono, c Inoolublo.
Complex
ANALYTICAL
TABLE 1
((6179) 6,09 (6.20) 4.82 (4.68) 10.24 (10.41) 6,96 (7.09) 6,77 (6,lb) 9.26 (8.94) 6.06 (6.37) 4.76 (6.61) 7.78 (7.77) 7.16 (6.66)
1.46 (1.47) 1,41 (1.37) 1.35 (1.34) 1.16 (1.16) 2.69 (2.47) 8.68 (8.65) 6.13 (6.49) 6.74
N
-
----
c
13Clb
287 (dec.) 210 (dec.)
182 (dec,) 163 (dac,)
29 29 29 32 27 21 28 22
2166 2166 2166 2166 2160 2100 2146 2140
>300
>a00
>300
243 (dco.)
r
220 (deo.) 26
2170
266 (dec. )
216 (dcc.) 26
26
2171
>300
263
192 (dot,)
203 (do&)
179 (dot,)
2170
20
26
2166 2160
30
2b
26
2160
2165
2166
195 (dcc,)
25
2166
112 b 62.9 a
lSB(doc.)
M& (“C)
47
AV (cm’*)
2177
WW complex (cm-l)
116 b
AM (ohm-l cm2 mol+)
365
Depending cm their subsequentuse these complexes were preparedeitherin benzeneor ~&XXX?by tseatingstuichiometricamonntsof the urgauutincomplex &R&I. with Al;cro, for 30 miu at room ~mp~rat~e. After ~&xMw&~ of the AgCl the filtratewas used for furtheEzeacticmswithout additions& fxe&merit.
To a s&&ion of Sn(O&lO$?h~ (0.5 mmol) in 25 ml of benzenewas klded Pd(CN)2(PPh3)2(0.3415 g, 0.5 mmol) in 40 ml of dicbloromethane.The microcrystaBineprecipitate,which was difficult to Elter of& was separatedby ~eu~~gatio~ and w_+hedwith hexane (70% yield)+
To a so&A&m of Q~~~~~~~ @I =+Ag, Q = ByN; M = Au, Q = K) (1 mmol) in 25 ml of acetonewas added an equimolecniarsolution of Sn(0&10.&3, in 25 mI of acetone, The immedi&eIy precipitatedwhite (or in the case of VIII y~~o~h) solid was filtered off and repeatedlywmhed with wa~r~ac~toue (yieids: complex VI, 63%; WI, 7643a;VE& 66% $X, 64%; X, 81%).
To a solution of I&[M(CN).J (1 mmol) in 10 ml of I&O and 15 ml of acetone was added a solution of Sn(O&lO,)& (2 rnmol) in acetcme(l/2 mole ratio).. Stirringwas continuedfor 3HO mb. The wZ&x.precipitatewas filtered off and washedwith benzeneor acet?ton.e and then with hexane (yields: complex XI, 81% XII, 88@&XIII, 85%; XIV, 91% xv, 81%; XVI, 93%).
366
{[R&z],[(p-NC)&e& (XVII, R = Bu; XVIII, R =Ih) The reaction was carried out as before by treating 1 mm01 of the iron com-
(vii)
plex with 3 mmol of the organotin perchlorato.complex. The resulting pounds were washed with acetone (yields; XVII, 95%; XVDI, 96%).
com-
References P. Royo. A. Laguna and J. Garcia. Rev. Acad. Cienaias Zaragoza. 28 (1973) 67;
1955. Sot..
(1963)
85; @)
H.C. Cla&
H. Kriegsmann and S. Pischtschan. 2. Anorg. AUg. Chem.. 308 (1961) 2l2. R. Okawxa, B-J. Hathaway and D.E. Webster, Proc. C&m. Sot.. (1963) 13. B-J. Hathaway and D-E. Webster. Rec. Chem. Sot.. (1963) 14. HX. Clark and R.J. O’Brien. Inorg. Chem.. 2 (1963) 1020. (a) R. Oka-. D.E. Webster gnd E.G. Rochow. J. Amer. Chem. Sot.. 82 <1960) 3278; Okawara and M. Oham, J. OrganometaL Chem.. 1 (1964) 360. R. Gassend. J.C. Maire and J.C. Pommier. J. OrganometaL Chem-. 132 (1977) 69. J. Madelshon. A. Marchand and J. V&de. J. OrganometaL Chem.. 6 (2.966) 25. R.C. Poller. Spectrochim. Acta. 22 (1966) 935. B.J. Hathaway and A.E. Underbill. Chem_ Sot.. (1961) 3091. R. Usdn, P. Royo and J. Forx&s, Rev. Acad. Ciencias. Zaragoza. 28 (1973) 349. J-H_ Bigelow. Inorganic Synth.. 2 (1946) 245. G. Brauer. Qufmica Inorganica heparativa, Ed. Reverti, Barcelona. 1958. P. 630.949.
R-J-
(b)
R.