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Reactions of Co2(CO)8 with potentially polydentate phosphines
Inorganicn
Chimicu
Reactions
Actu,
182 (1991) 55-58
of co2(c0)8
C. Moreno,
Ma. J. Macazaga
Departamento
de Q&mica
with potentially
polydentate
phosphines
and S. Delgado*
(Inorga’nica),
Universidad
Autdnoma
de Madrid,
Canto
Blanco,
28049 Madrid
(Spain)
(Received September 26, 1990)
Abstract
reacts with potentially polydentate phosphines such as PhzPpy (2-(diphenylphosphino)pyridine), t-dppv (puns-1,2-vinylenebis(diphenylphosphine)), dppa (bis(diphenylphosphino)amine) and dpmp (bis((diphenylphosphino)methyl)phenylphosihine) to give Co,(CO)& (L=Ph,Ppy and t-dppv), Coz(CO),(dppa) and Coz(CO)s(dpmp) where the ligands behave as mono-, di- and tridentate,respectively, vikthe ionic intermediates’[Co2(C0)3~][Co(C0)4] (L= Ph,Ppy and t-dppv) and [COUP P][Co(CO),] (P P = dppa and dpmp). All the compounds have been characterized by elemental analysis, IR, electronic, ‘H and 31P NMR spectroscopy. COAX
Introduction
The reactions of dicobalt octacarbonyl with Lewis bases give rise to different products, depending on the nature of the base and reaction conditions. With monodentate phosphines the usual initial product is [Co(CO),_,IJ[Co(CO),] [l], where the value of n is dependent on the base [2]; most usually n =2. This salt can be converted to the dinuclear species, Co,(CO)s_,L, by heating in refluxing benzene. Much of the interest in the substitution reactions of cobalt carbonyls stems from modification of the hydroformylation catalyst HCO(CO)~ with phosphine ligands [3]. With bis(tertiary phospgnes) it yields complexes of the formula CO~(CO)~(P P) [4]. Few of them have been characterized in the solid state and in solution [4, 51. The present work describes the reactions of COAX with nucleophiles such as PhzPpy, t-dppv, dppa and dpmp which can behave as mono-, bi- or tridentate ligands.
Dicobalt octacarbonyl was obtained from Fluka and used without further purification. The reagents PhzPpy [6], dppa [7], t-dppv [8] and dpmp [9] were prepared according to the literature and characterized by their IR and NMR spectra. The melting points and elemental analyses were in good agreement with the reported values. Elemental analyses were performed by the Microanalytical Laboratory of this Department. The cobalt was determined by titration of the Co-EDTA complex in the presence of NET as indicator. The IR spectra were recorded in the range 4000-200 cm- ’ on a Nicolet 5DX FT-IR spectrometer using Nujol and hexachlorobutadiene mulls between CsI windows, KJ3r plates or in CHZCll solution. ‘H and 31P NMR spectra were obtained on a Bruker WI-I-200-SY instrument. All ‘H NMR chemical shifts are relative to TMS. 31P chemical shifts are quoted relative to 85% H3P04. The visible spectra were recorded on a Pye Unicam SP 8-100 ultraviolet spectrophotometer. Preparation of c~,(CO)~(Ph~Ppy)z
Experimental
All manipulations were carried out using standard Schlenk techniques under an atmosphere of dry nitrogen. CHzClz was dried over and distilled from P&&o. Hexane was dried over and distilled from sodium benzophenone ketyl. *Author to whom correspondence should be addressed.
0020-1693/91/$3.50
To a 30 ml CHzClz solution of Co2(CO)s (2 g, 5.85 mmol) in a nitrogen-filled 100 ml Schlenk flask was added another solution of PhzPpy (3.08 g, 0.012 mol) in the same solvent. An orange-red solid immediately appeared, and evolution of CO was observed. After 29 h, the reaction solution was filtered. The resulting orange-red solid was washed with cold n-hexane and dried under vacuum. The yield was 4.28 g (90%). Anal. Calc. for C&28NZ06PZC~2: C, 59.08; H, 3.45; N, 3.45; Co, 14.51. Found: C, 59.02;
0 Elsevier
Sequoia/Printed
in Switzerland
repulsive interactions and weaken the metal-metal bond 1231. The u+ 6* transitions decrease in energy according to Co,(CO)s> Co2(CO)& COY (dpmp) > (& or Dsh symmetry) and Cogs> Coz(COMdppa)
(G,
9 R. Appel,
10 11
symmetry). 12 13
Acknowledgement
We thank Dr Jestis H. Rodriguez 31P NMR spectra.
Ramos for the
References
14 15
16 17
G. Wilkinson, F. G. A. Stone and W. E. Abel (eds.), Comprehensive Organometallic Chemistry, Vol. 5, Pergamon, Gxford, 1982. (a) F. Ungvary and L. Marko, Inorg. Chim. Acta, 4 (1970) 324; (b) (1970); J. Organomet. Chem., 71 (1974) 283. R. L. Pruett, Adv. Organomet. Chem., 17 (1979) 1. (a) W. Harrison and J. Trotter,1 Chem. Sot. A, (1971) 1607; (b) D. J. Thornhill and A. R. Manning, J. Chem. Sot., Dalton Trans., (1973) 2086; (c) E. C. Lisic and B. E. Hanson, Inorg Chem., 25 (1986) 812. T. Fukumoto, Y. Matsumura and R. Okwara, J. Organomet. Gem., 69 (1974) 437. A. Maisonnet, J. P. Farr, M. M. Olmstead, C. T. Hunt and A. L. Balch, Inorg. Chem., 21 (1982) 3961. H. Nbth and L. Maine], Z. Anorg. Allg. Chem., 349 (1967) 225. A. M. Aguiar and D. Daigle, J. Am. Chem. Sot., 86 (1964) 2299.
18
19
20 21 22
23
K. Geisler and H. F. Scholer, Chem. Ber., 112 (1979) 648. J. Ellermann, N. Geheeb, G. Zoubek and G. Thiele, Z. Naturfosch., Teil B, 32 (1977) 1271. M. Absi-Habi, J. D. Atwood, P. N. Forbus and T. L. Brown, J. Am. Chem. Sot,, IO2 (1980) 6248. M. F. Mirbach, M. J. Mirbach and R. W. Wegman, Organometallics, 90 (1984) 3. K. Y. Lee and J. K. Kochi, Znorg. Chem., 28 (1989) 567. N. P. Forbus and T. L. Brown, Znorg. Chem., 20 (1981) 4313. H. G. Horn and K. Sommer, Spectrochim. Acta, Part A, 27 (1971) 1049; M. Bacci, Spectrochim. Acta, Part A, 28 (1972) 2286. R. U&n, J. Fomies, R. Navarro and J. I. Cebollada, J. Organomet. Chem., 304 (1986) 381. (a) A. R. Manning, J. Chem. Sot. A, (1968) 1135; (b) A. R. Manning and J. R. Miller, J. Chem. Sot. A, (1970) 3352. (a) A. R. Manning, J. Chem. Sot. A, (1968) 1018; (b) D. de Montauzon and R. Poilblanc, J. Organomet. Chem., 54 (1973) 291, and refs. therein. J.P. Crow and R. Cullen, Znorg Chem., 10 (1971) 2165; W. R. Cullen, J. Crow, W. Harrison and J. Trotter, J. Am. Chem. Sot., 92 (1970) 6339. C. Pegot and M. R. Poilblanc, C. R. Acad. Sci. Paris, 268C, (1969) 955. W. G. Sly, J. Am. Chem. Sot., 81 (1959) 18. (a) H. B. Abrahamson, C. C. Frazier, D. S. Ginley, H. B. Gray, J. Librenthal, D. R. Tyler and M. S. Wrighton, Znorg. Chem., 16 (1977) 1554; (b) R. W. Wegman and T. L. Brown, Inorg Chem., 22 (1983) 183; (c) A. J. Poe and R. A. Jackson, Inorg. Chem., I7 (1978) 2330, and refs. therein. R. A. Levenson and H. B. Gray, J. Am. Chem. Sot., 97 (1975) 6042.
Chimicu
Reactions
Actu,
182 (1991) 55-58
of co2(c0)8
C. Moreno,
Ma. J. Macazaga
Departamento
de Q&mica
with potentially
polydentate
phosphines
and S. Delgado*
(Inorga’nica),
Universidad
Autdnoma
de Madrid,
Canto
Blanco,
28049 Madrid
(Spain)
(Received September 26, 1990)
Abstract
reacts with potentially polydentate phosphines such as PhzPpy (2-(diphenylphosphino)pyridine), t-dppv (puns-1,2-vinylenebis(diphenylphosphine)), dppa (bis(diphenylphosphino)amine) and dpmp (bis((diphenylphosphino)methyl)phenylphosihine) to give Co,(CO)& (L=Ph,Ppy and t-dppv), Coz(CO),(dppa) and Coz(CO)s(dpmp) where the ligands behave as mono-, di- and tridentate,respectively, vikthe ionic intermediates’[Co2(C0)3~][Co(C0)4] (L= Ph,Ppy and t-dppv) and [COUP P][Co(CO),] (P P = dppa and dpmp). All the compounds have been characterized by elemental analysis, IR, electronic, ‘H and 31P NMR spectroscopy. COAX
Introduction
The reactions of dicobalt octacarbonyl with Lewis bases give rise to different products, depending on the nature of the base and reaction conditions. With monodentate phosphines the usual initial product is [Co(CO),_,IJ[Co(CO),] [l], where the value of n is dependent on the base [2]; most usually n =2. This salt can be converted to the dinuclear species, Co,(CO)s_,L, by heating in refluxing benzene. Much of the interest in the substitution reactions of cobalt carbonyls stems from modification of the hydroformylation catalyst HCO(CO)~ with phosphine ligands [3]. With bis(tertiary phospgnes) it yields complexes of the formula CO~(CO)~(P P) [4]. Few of them have been characterized in the solid state and in solution [4, 51. The present work describes the reactions of COAX with nucleophiles such as PhzPpy, t-dppv, dppa and dpmp which can behave as mono-, bi- or tridentate ligands.
Dicobalt octacarbonyl was obtained from Fluka and used without further purification. The reagents PhzPpy [6], dppa [7], t-dppv [8] and dpmp [9] were prepared according to the literature and characterized by their IR and NMR spectra. The melting points and elemental analyses were in good agreement with the reported values. Elemental analyses were performed by the Microanalytical Laboratory of this Department. The cobalt was determined by titration of the Co-EDTA complex in the presence of NET as indicator. The IR spectra were recorded in the range 4000-200 cm- ’ on a Nicolet 5DX FT-IR spectrometer using Nujol and hexachlorobutadiene mulls between CsI windows, KJ3r plates or in CHZCll solution. ‘H and 31P NMR spectra were obtained on a Bruker WI-I-200-SY instrument. All ‘H NMR chemical shifts are relative to TMS. 31P chemical shifts are quoted relative to 85% H3P04. The visible spectra were recorded on a Pye Unicam SP 8-100 ultraviolet spectrophotometer. Preparation of c~,(CO)~(Ph~Ppy)z
Experimental
All manipulations were carried out using standard Schlenk techniques under an atmosphere of dry nitrogen. CHzClz was dried over and distilled from P&&o. Hexane was dried over and distilled from sodium benzophenone ketyl. *Author to whom correspondence should be addressed.
0020-1693/91/$3.50
To a 30 ml CHzClz solution of Co2(CO)s (2 g, 5.85 mmol) in a nitrogen-filled 100 ml Schlenk flask was added another solution of PhzPpy (3.08 g, 0.012 mol) in the same solvent. An orange-red solid immediately appeared, and evolution of CO was observed. After 29 h, the reaction solution was filtered. The resulting orange-red solid was washed with cold n-hexane and dried under vacuum. The yield was 4.28 g (90%). Anal. Calc. for C&28NZ06PZC~2: C, 59.08; H, 3.45; N, 3.45; Co, 14.51. Found: C, 59.02;
0 Elsevier
Sequoia/Printed
in Switzerland
repulsive interactions and weaken the metal-metal bond 1231. The u+ 6* transitions decrease in energy according to Co,(CO)s> Co2(CO)& COY (dpmp) > (& or Dsh symmetry) and Cogs> Coz(COMdppa)
(G,
9 R. Appel,
10 11
symmetry). 12 13
Acknowledgement
We thank Dr Jestis H. Rodriguez 31P NMR spectra.
Ramos for the
References
14 15
16 17
G. Wilkinson, F. G. A. Stone and W. E. Abel (eds.), Comprehensive Organometallic Chemistry, Vol. 5, Pergamon, Gxford, 1982. (a) F. Ungvary and L. Marko, Inorg. Chim. Acta, 4 (1970) 324; (b) (1970); J. Organomet. Chem., 71 (1974) 283. R. L. Pruett, Adv. Organomet. Chem., 17 (1979) 1. (a) W. Harrison and J. Trotter,1 Chem. Sot. A, (1971) 1607; (b) D. J. Thornhill and A. R. Manning, J. Chem. Sot., Dalton Trans., (1973) 2086; (c) E. C. Lisic and B. E. Hanson, Inorg Chem., 25 (1986) 812. T. Fukumoto, Y. Matsumura and R. Okwara, J. Organomet. Gem., 69 (1974) 437. A. Maisonnet, J. P. Farr, M. M. Olmstead, C. T. Hunt and A. L. Balch, Inorg. Chem., 21 (1982) 3961. H. Nbth and L. Maine], Z. Anorg. Allg. Chem., 349 (1967) 225. A. M. Aguiar and D. Daigle, J. Am. Chem. Sot., 86 (1964) 2299.
18
19
20 21 22
23
K. Geisler and H. F. Scholer, Chem. Ber., 112 (1979) 648. J. Ellermann, N. Geheeb, G. Zoubek and G. Thiele, Z. Naturfosch., Teil B, 32 (1977) 1271. M. Absi-Habi, J. D. Atwood, P. N. Forbus and T. L. Brown, J. Am. Chem. Sot,, IO2 (1980) 6248. M. F. Mirbach, M. J. Mirbach and R. W. Wegman, Organometallics, 90 (1984) 3. K. Y. Lee and J. K. Kochi, Znorg. Chem., 28 (1989) 567. N. P. Forbus and T. L. Brown, Znorg. Chem., 20 (1981) 4313. H. G. Horn and K. Sommer, Spectrochim. Acta, Part A, 27 (1971) 1049; M. Bacci, Spectrochim. Acta, Part A, 28 (1972) 2286. R. U&n, J. Fomies, R. Navarro and J. I. Cebollada, J. Organomet. Chem., 304 (1986) 381. (a) A. R. Manning, J. Chem. Sot. A, (1968) 1135; (b) A. R. Manning and J. R. Miller, J. Chem. Sot. A, (1970) 3352. (a) A. R. Manning, J. Chem. Sot. A, (1968) 1018; (b) D. de Montauzon and R. Poilblanc, J. Organomet. Chem., 54 (1973) 291, and refs. therein. J.P. Crow and R. Cullen, Znorg Chem., 10 (1971) 2165; W. R. Cullen, J. Crow, W. Harrison and J. Trotter, J. Am. Chem. Sot., 92 (1970) 6339. C. Pegot and M. R. Poilblanc, C. R. Acad. Sci. Paris, 268C, (1969) 955. W. G. Sly, J. Am. Chem. Sot., 81 (1959) 18. (a) H. B. Abrahamson, C. C. Frazier, D. S. Ginley, H. B. Gray, J. Librenthal, D. R. Tyler and M. S. Wrighton, Znorg. Chem., 16 (1977) 1554; (b) R. W. Wegman and T. L. Brown, Inorg Chem., 22 (1983) 183; (c) A. J. Poe and R. A. Jackson, Inorg. Chem., I7 (1978) 2330, and refs. therein. R. A. Levenson and H. B. Gray, J. Am. Chem. Sot., 97 (1975) 6042.