- Email: [email protected]
Tris(2-dimethylaminoethyl)amine complexes of the group IV a metal tetrachlorides
INORG. NUCL. CHEM. LETTERS Vol.14, pp. 363-366, 1978.
Pergamon Press.
TRIS (2 - D I M E T H Y L A M I N O E T H Y L ) A M I N E COMPLEXES OF THE GROUP IV A M E T A L T E T R A C H L O R I D E S S. R. Wade and G. R. Willey D e p a r t m e n t of C h e m i s t r y and M o l e c u l a r Sciences, U n i v e r s i t y of Warwick, C o v e n t r y CV4 7A L
(Received 3 July 1978; received for publication 3 August 1978) INTRODUCTION C o m p l e x e s of the Group IV A m e t a l t e t r a c h l 0 r i d e s with m u l t i d e n t a t e ligands a r e u s u a l l y six c o o r d i n a t e MX 4. B o r eight c o o r d i n a t e
MX 4. 2B
(B = b i d e n t a t e ligand) ; a few s e v e n c o o r d i n a t e MX 4. T (T = t e r d e n t a t e ligand) c o m p l e x e s have b e e n noted. (1) T r i s (2 - d i m e t h y l a m i n o e t h y l ) a m i n e ( M e 6 t r e n ) is a tripod ligand well known for i t s c o m p l e x e s with the l a t e r t r a n s i t i o n m e t a l s in w h i c h all four n i t r o g e n c e n t r e s a r e c o o r d i n a t e d . (2) F o r the e a r l i e r m e t a l s , a d d u c t s with Ti(III) and C r (III) c h l o r i d e s have r e c e n t l y b e e n d e s c r i b e d which f e a t u r e the ligand in a t e r d e n t a t e c a p a c i t y . (3) We now r e p o r t the c o r r e s p o n d i n g 1 : 1 c o m p l e x e s with the t e t r a h a l i d e s MC14 (M = Ti, Zr and Hf).
N e i t h e r high ( > 6 ) c o o r d i n a t i o n n o r r e d u c e d
d e n t i c i t y is in e v i d e n c e .
EXPERIMENTAL All r e a c t i o n s w e r e c a r r i e d out u n d e r a s t r i c t n i t r o g e n at m o s p h e r e . Addition of M e 6 t r e n to the a p p r o p r i a t e m e t a l t e t r a c h l o r i d e in b e n z e n e s o l u t i o n s gave i m m e d i a t e r e a c t i o n with p r e c i p i t a t i o n of the r e s p e c t i v e m o n o adduct MC14. M e 6 t r e n .
T h e s e w e r e w a s h e d thoroughly with b e n z e n e and
n - hexane, pumped in vacuo (T = 300 K) f o r s e v e r a l h o u r s and then s e a l e d in glass ampoules under nitrogen. (a) t i t a n i u m
D r o p w i s e addition of M e 6 t r e n (4.6g, 2 0 . 0 m tool) to TiC14
(1.17g, 9 . 0 m m o l ) gave p a l e - g r e e n TiC14. M e 6 t r e n (3.3g, 88~o). Anal. Calcd for C12H30N4C14Ti : C , 3 4 . 3 ; H, 7 . 2 ; N, 1 3 . 3 ; C1, 33.7. Found.
C, 3 4 . 4 ; H, 7.1 ; N, 1 3 . 0 ; C1, 3 3 . 3
I r b a n d s : 3018 ( w ) , 2 9 5 0 ( s ) ,
2925 ( s ) , 2828 ( m ) , 2808 ( w ) , 1474 ( w ) ,
1461 ( s ) ,
1400(w),
1439 ( w ) , 1 4 3 6 ( w ) ,
1259 ( m ) ,
1237(w),
1208 ( w ) , 1 1 6 6 ( w ) ,
1040(m),
1020 ( m ) , 1004 ( m ) ,
1375 ( w ) , 1 3 0 0 ( w ) ,
1279(m),
1112 ( w ) , 1063 ( w ) , 1052 (w),
980(m),
894 ( s ) , 803 ( m ) , 781 ( s ) , 765 ( w ) , 746 (m) , 724 (m) , 387 (s) , 356 (s) , 187 ( m ) c m -1 r e s p e c t i v e l y , H 1 n m r 363
Printed in Great Britain
364
Amine Complexes
(CD2C12, 8ppm (TMS)) 2 . 6 0 , 2.82 (multiplet), 3.51 (multiplet) (b) zirconium
Similarly, addition of Me6tren (2, 2g, 11.0 m mot) to
ZrC14. 2NMe3(I. 6g, 4.7 m tool) gave white ZrC14. Me6tren (1.8g, 84%) with release of trimethylamine. Anal. Calcdfor C12H30N4C14Zr. C, 31.1 ; H, 6 . 5 ; N, 1 2 . 0 ; C1, 30.6 Found. C, 3 0 . 8 ; H, 6 . 8 ; N, 1 1 . 8 ; C 1 , 29.9 Ir bands : 3020 (m), 2952 (s), 2930 (s), 2845 (m), 2820 (w), 1475 (w), 1470 (s), 1458 (w), 1435 (w), 1403 (m), 1288 (m), 1 2 ~ (w), 1209 (w), 1166 (w), 1125 (w), 1108 (w), 1076 (w), 1063 (w), 1041 (s), 1000 (w), 9 9 0 ( s ) , 910(w), 8 0 1 ( m ) , 7 8 6 ( s ) , 7 6 4 ( s ) , 735 (w), 7 1 9 ( m ) , 6 8 3 ( s ) , 372 (s), 318 (s), 168 ( m ) , cm "I respectively.
Hlnmr(CD2CI2 , ~ppm(TMS))
2.68, 2.92 (multiplet) and 3.51(multiplet)
(c) hafnium
Similarly, addition of Me6tren (1.3g, 5.5 m tool) to HfC14.
2NMe 3 (1. lg, 2.5 m tool) gave white HfCl~Me6tren (1.2g, 88%) with release of trimethylamine. Anal. CalcdforC12H30N4C14Hf. C, 26.1 ; H, 5 . 5 ; N , Found. C, 2 5 . 8 ; H, 5 . 7 ; N , Irbands:3130(w),
10.1 ; C1, 25.8
9 . 8 ; CI, 25.3
3020(w), 2955 (s), 2940(s), 2855 (m), 2820(w),
1480 (w), 1470 (s), 1463 (w), 1445 (w), 1412 (w), 1378 (w), 1308 (w), 1295 (w), 1265 (rr/), 1230 (w), 1213 (w), I156 (w), ll00 (w), 1085 (m), 1053 (w), 1037(m), 1005 (s), 9 3 7 ( s ) , 915 (w), 8 1 5 ( m ) , 785 (s), 763 (m), 725 (m), -I 680 (w), 327 (s), 277 (s), 143 (m) cm respectively. Hlnmr (CD2C12 8 ppm (TMS)) 2. 70, 2.97 (multiplet) 3.52 (multiplet) Ir spectra were recorded using Perkin Elmer 621 and Fourier FS 720 spectrophotometers with samples as mulls.
Proton nmr spectra (90 MHz)
were obtained at 230K using a Br~ker WH90 spectrometer. analyses were performed commercially.
C , H and N
Chloride was estimated using
the Volhard titration. RESULTS AND DISCUSSION Reaction in benzene solutions of a twofold excess of Me6tren either directly with MC14(M = Ti) or by ligand replacement with MC14. 2NMe 3 4 (M = Zr and Hi'gives only the 1 : 1 complexes formulated as [ MC12. Me6tren ] 2+2C1". The products are extremely air-moisture sensitive and insoluble in most organic solvents.
The slight solubility in CH2CI2 and
CH3NO 2 gives solutions which decompose quickly ( ~ 2 rains) at room
365
Amine Complexes
t e m p e r a t u r e but slowly enough at 230K to allow 1H n m r m e a s u r e m e n t s . Conducting s t u d i e s p r o v e d c o m p l e t e l y u n r e l i a b l e .
E v i d e n c e for the p r o p o s e d
six c o o r d i n a t e s t r u c t u r e
2*
\
2cl\
t
"3 cH3
m
CH
. .
el --
z
i n v o l v i n g the ligand in i t s n o r m a l t e t r a d e n t a t e r o l e can be s u m m a r i s e d a s follows: The 1H n m r s p e c t r a show two c o m p l e x m u l t i p l e t s f o r the m e t h y l e n e backbone and one s h a r p s i g n a l for e q u i v a l e n t t e r m i n a l -NMe 2 p r o t o n s .
The
l a t t e r 8 2 . 6 0 ppm ( T i ) , 6 2.68 ppm ( Z r ) and 8 2 . 7 0 ppm (l-if)reflect a p r o g r e s s i v e shift to low field, ~ 2 . 3 2 ppm for neat M e 6 t r e n , c o m m e n s u r a t e with Me2N ---->M bonding.
The a b s e n c e of ~(CH) b a n d s a s s o c i a t e d with u n c o o r d i n a t e d ligand NMe 2 -1 g r o u p s in the 2820 - 2760 c m r e g i o n (6). -1 The p r e s e n c e of two s t r o n g b a n d s in the 400 - 300 c m r e g i o n of the far i r v(TiC1) 387, 356
v(ZrC1) 372, 318 and ~(HfC1) 3 2 7 , 277 c m "1 is
typical of six c o o r d i n a t e M( IV ) s p e c i e s (C2v) with two c i s - c h l o r i n e a t o m s . (7) -1 Splitting of the i n t e n s e 796 c m s k e l e t o n a l CH 2 r o c k i n g mode of the ligand which o c c u r s on the f o r m a t i o n of a 5 - m e m b e r e d fused c h e l a t e r i n g -1 (8) (9) (10) is o b s e r v e d throughout, (M = Ti) 803, 781 c m ; (M = Z r ) -1 -1 801, 786 c m ; (M = Hf) 815, 785 c m . Such r i n g f o r m a t i o n is m u c h f a v o u r e d on t h e r m o d y n a m i c g r o u n d s .
(11)
S i m i l a r r e a c t i o n s of TiCI 4 and MCI 4. 2NMe3(M = Z r and Hf) u s i n g the p a r e n t t r e n and a l s o the n o n - t r i p o d t e t r e n a s p o t e n t i a l t e t r a d e n t a t e N - d o n o r s give n o n - s t o i c h i o m e t r i c ( p o l y m e r i c ) p r o d u c t s .
Acknowledgement
We w i s h to thank the S . R . C . for f i n a n c i a l s u p p o r t (SRW)
366
Amine Complexes
REFERENCES 1
D. L. KEPERT, 'The Early Transitton M e t a l s ' , Academic Press, 1972
2
See e . g . M . C IAMPOLINI, N. NARDI and G.P. SPERONI, Co-ord. Chem. Revs., l , 222 (1966)
3
~. HUGHES and G. R. WILLEY, Inorg. Chim. Acta, I._33, L1 (1975)
4
J. HUGHES and G.R. WILLEY, Inorg. Chim. Acta, 2 0 , 137 (1976)
5
G. R. WILLEY, Inorg. Chim. Acta, 2 1 , L12 (1977)
6
I~. A. BALDWIN and G. J. LEIGH, J. Chem. Soc. (A), 1431 (1968)
7 A. FINCH, P.N. GATES, K. R A D C L I F F E , F. N. DICKSON and F. F. BENTLEY, 'Chemical Applications of F a r Infrared Spectroscopy', Academic Press, 1970 8
M. E. BALDWIN, J. Chem. Soc., 4369 (1960)
9
D . A . BUCKINGHAM and D. JONES, Laorg. Chem., 4_, 1387 (1965)
l0 S. K. MADAN and J. PEONE , Inorg. Chem., 6 , 463 (1967) ll
P. PAOLETTI, L. FABBRIZZI and R. BARBUCCI, Inorg. Chim. Acta Revs., Z , 43 (1973)
Pergamon Press.
TRIS (2 - D I M E T H Y L A M I N O E T H Y L ) A M I N E COMPLEXES OF THE GROUP IV A M E T A L T E T R A C H L O R I D E S S. R. Wade and G. R. Willey D e p a r t m e n t of C h e m i s t r y and M o l e c u l a r Sciences, U n i v e r s i t y of Warwick, C o v e n t r y CV4 7A L
(Received 3 July 1978; received for publication 3 August 1978) INTRODUCTION C o m p l e x e s of the Group IV A m e t a l t e t r a c h l 0 r i d e s with m u l t i d e n t a t e ligands a r e u s u a l l y six c o o r d i n a t e MX 4. B o r eight c o o r d i n a t e
MX 4. 2B
(B = b i d e n t a t e ligand) ; a few s e v e n c o o r d i n a t e MX 4. T (T = t e r d e n t a t e ligand) c o m p l e x e s have b e e n noted. (1) T r i s (2 - d i m e t h y l a m i n o e t h y l ) a m i n e ( M e 6 t r e n ) is a tripod ligand well known for i t s c o m p l e x e s with the l a t e r t r a n s i t i o n m e t a l s in w h i c h all four n i t r o g e n c e n t r e s a r e c o o r d i n a t e d . (2) F o r the e a r l i e r m e t a l s , a d d u c t s with Ti(III) and C r (III) c h l o r i d e s have r e c e n t l y b e e n d e s c r i b e d which f e a t u r e the ligand in a t e r d e n t a t e c a p a c i t y . (3) We now r e p o r t the c o r r e s p o n d i n g 1 : 1 c o m p l e x e s with the t e t r a h a l i d e s MC14 (M = Ti, Zr and Hf).
N e i t h e r high ( > 6 ) c o o r d i n a t i o n n o r r e d u c e d
d e n t i c i t y is in e v i d e n c e .
EXPERIMENTAL All r e a c t i o n s w e r e c a r r i e d out u n d e r a s t r i c t n i t r o g e n at m o s p h e r e . Addition of M e 6 t r e n to the a p p r o p r i a t e m e t a l t e t r a c h l o r i d e in b e n z e n e s o l u t i o n s gave i m m e d i a t e r e a c t i o n with p r e c i p i t a t i o n of the r e s p e c t i v e m o n o adduct MC14. M e 6 t r e n .
T h e s e w e r e w a s h e d thoroughly with b e n z e n e and
n - hexane, pumped in vacuo (T = 300 K) f o r s e v e r a l h o u r s and then s e a l e d in glass ampoules under nitrogen. (a) t i t a n i u m
D r o p w i s e addition of M e 6 t r e n (4.6g, 2 0 . 0 m tool) to TiC14
(1.17g, 9 . 0 m m o l ) gave p a l e - g r e e n TiC14. M e 6 t r e n (3.3g, 88~o). Anal. Calcd for C12H30N4C14Ti : C , 3 4 . 3 ; H, 7 . 2 ; N, 1 3 . 3 ; C1, 33.7. Found.
C, 3 4 . 4 ; H, 7.1 ; N, 1 3 . 0 ; C1, 3 3 . 3
I r b a n d s : 3018 ( w ) , 2 9 5 0 ( s ) ,
2925 ( s ) , 2828 ( m ) , 2808 ( w ) , 1474 ( w ) ,
1461 ( s ) ,
1400(w),
1439 ( w ) , 1 4 3 6 ( w ) ,
1259 ( m ) ,
1237(w),
1208 ( w ) , 1 1 6 6 ( w ) ,
1040(m),
1020 ( m ) , 1004 ( m ) ,
1375 ( w ) , 1 3 0 0 ( w ) ,
1279(m),
1112 ( w ) , 1063 ( w ) , 1052 (w),
980(m),
894 ( s ) , 803 ( m ) , 781 ( s ) , 765 ( w ) , 746 (m) , 724 (m) , 387 (s) , 356 (s) , 187 ( m ) c m -1 r e s p e c t i v e l y , H 1 n m r 363
Printed in Great Britain
364
Amine Complexes
(CD2C12, 8ppm (TMS)) 2 . 6 0 , 2.82 (multiplet), 3.51 (multiplet) (b) zirconium
Similarly, addition of Me6tren (2, 2g, 11.0 m mot) to
ZrC14. 2NMe3(I. 6g, 4.7 m tool) gave white ZrC14. Me6tren (1.8g, 84%) with release of trimethylamine. Anal. Calcdfor C12H30N4C14Zr. C, 31.1 ; H, 6 . 5 ; N, 1 2 . 0 ; C1, 30.6 Found. C, 3 0 . 8 ; H, 6 . 8 ; N, 1 1 . 8 ; C 1 , 29.9 Ir bands : 3020 (m), 2952 (s), 2930 (s), 2845 (m), 2820 (w), 1475 (w), 1470 (s), 1458 (w), 1435 (w), 1403 (m), 1288 (m), 1 2 ~ (w), 1209 (w), 1166 (w), 1125 (w), 1108 (w), 1076 (w), 1063 (w), 1041 (s), 1000 (w), 9 9 0 ( s ) , 910(w), 8 0 1 ( m ) , 7 8 6 ( s ) , 7 6 4 ( s ) , 735 (w), 7 1 9 ( m ) , 6 8 3 ( s ) , 372 (s), 318 (s), 168 ( m ) , cm "I respectively.
Hlnmr(CD2CI2 , ~ppm(TMS))
2.68, 2.92 (multiplet) and 3.51(multiplet)
(c) hafnium
Similarly, addition of Me6tren (1.3g, 5.5 m tool) to HfC14.
2NMe 3 (1. lg, 2.5 m tool) gave white HfCl~Me6tren (1.2g, 88%) with release of trimethylamine. Anal. CalcdforC12H30N4C14Hf. C, 26.1 ; H, 5 . 5 ; N , Found. C, 2 5 . 8 ; H, 5 . 7 ; N , Irbands:3130(w),
10.1 ; C1, 25.8
9 . 8 ; CI, 25.3
3020(w), 2955 (s), 2940(s), 2855 (m), 2820(w),
1480 (w), 1470 (s), 1463 (w), 1445 (w), 1412 (w), 1378 (w), 1308 (w), 1295 (w), 1265 (rr/), 1230 (w), 1213 (w), I156 (w), ll00 (w), 1085 (m), 1053 (w), 1037(m), 1005 (s), 9 3 7 ( s ) , 915 (w), 8 1 5 ( m ) , 785 (s), 763 (m), 725 (m), -I 680 (w), 327 (s), 277 (s), 143 (m) cm respectively. Hlnmr (CD2C12 8 ppm (TMS)) 2. 70, 2.97 (multiplet) 3.52 (multiplet) Ir spectra were recorded using Perkin Elmer 621 and Fourier FS 720 spectrophotometers with samples as mulls.
Proton nmr spectra (90 MHz)
were obtained at 230K using a Br~ker WH90 spectrometer. analyses were performed commercially.
C , H and N
Chloride was estimated using
the Volhard titration. RESULTS AND DISCUSSION Reaction in benzene solutions of a twofold excess of Me6tren either directly with MC14(M = Ti) or by ligand replacement with MC14. 2NMe 3 4 (M = Zr and Hi'gives only the 1 : 1 complexes formulated as [ MC12. Me6tren ] 2+2C1". The products are extremely air-moisture sensitive and insoluble in most organic solvents.
The slight solubility in CH2CI2 and
CH3NO 2 gives solutions which decompose quickly ( ~ 2 rains) at room
365
Amine Complexes
t e m p e r a t u r e but slowly enough at 230K to allow 1H n m r m e a s u r e m e n t s . Conducting s t u d i e s p r o v e d c o m p l e t e l y u n r e l i a b l e .
E v i d e n c e for the p r o p o s e d
six c o o r d i n a t e s t r u c t u r e
2*
\
2cl\
t
"3 cH3
m
CH
. .
el --
z
i n v o l v i n g the ligand in i t s n o r m a l t e t r a d e n t a t e r o l e can be s u m m a r i s e d a s follows: The 1H n m r s p e c t r a show two c o m p l e x m u l t i p l e t s f o r the m e t h y l e n e backbone and one s h a r p s i g n a l for e q u i v a l e n t t e r m i n a l -NMe 2 p r o t o n s .
The
l a t t e r 8 2 . 6 0 ppm ( T i ) , 6 2.68 ppm ( Z r ) and 8 2 . 7 0 ppm (l-if)reflect a p r o g r e s s i v e shift to low field, ~ 2 . 3 2 ppm for neat M e 6 t r e n , c o m m e n s u r a t e with Me2N ---->M bonding.
The a b s e n c e of ~(CH) b a n d s a s s o c i a t e d with u n c o o r d i n a t e d ligand NMe 2 -1 g r o u p s in the 2820 - 2760 c m r e g i o n (6). -1 The p r e s e n c e of two s t r o n g b a n d s in the 400 - 300 c m r e g i o n of the far i r v(TiC1) 387, 356
v(ZrC1) 372, 318 and ~(HfC1) 3 2 7 , 277 c m "1 is
typical of six c o o r d i n a t e M( IV ) s p e c i e s (C2v) with two c i s - c h l o r i n e a t o m s . (7) -1 Splitting of the i n t e n s e 796 c m s k e l e t o n a l CH 2 r o c k i n g mode of the ligand which o c c u r s on the f o r m a t i o n of a 5 - m e m b e r e d fused c h e l a t e r i n g -1 (8) (9) (10) is o b s e r v e d throughout, (M = Ti) 803, 781 c m ; (M = Z r ) -1 -1 801, 786 c m ; (M = Hf) 815, 785 c m . Such r i n g f o r m a t i o n is m u c h f a v o u r e d on t h e r m o d y n a m i c g r o u n d s .
(11)
S i m i l a r r e a c t i o n s of TiCI 4 and MCI 4. 2NMe3(M = Z r and Hf) u s i n g the p a r e n t t r e n and a l s o the n o n - t r i p o d t e t r e n a s p o t e n t i a l t e t r a d e n t a t e N - d o n o r s give n o n - s t o i c h i o m e t r i c ( p o l y m e r i c ) p r o d u c t s .
Acknowledgement
We w i s h to thank the S . R . C . for f i n a n c i a l s u p p o r t (SRW)
366
Amine Complexes
REFERENCES 1
D. L. KEPERT, 'The Early Transitton M e t a l s ' , Academic Press, 1972
2
See e . g . M . C IAMPOLINI, N. NARDI and G.P. SPERONI, Co-ord. Chem. Revs., l , 222 (1966)
3
~. HUGHES and G. R. WILLEY, Inorg. Chim. Acta, I._33, L1 (1975)
4
J. HUGHES and G.R. WILLEY, Inorg. Chim. Acta, 2 0 , 137 (1976)
5
G. R. WILLEY, Inorg. Chim. Acta, 2 1 , L12 (1977)
6
I~. A. BALDWIN and G. J. LEIGH, J. Chem. Soc. (A), 1431 (1968)
7 A. FINCH, P.N. GATES, K. R A D C L I F F E , F. N. DICKSON and F. F. BENTLEY, 'Chemical Applications of F a r Infrared Spectroscopy', Academic Press, 1970 8
M. E. BALDWIN, J. Chem. Soc., 4369 (1960)
9
D . A . BUCKINGHAM and D. JONES, Laorg. Chem., 4_, 1387 (1965)
l0 S. K. MADAN and J. PEONE , Inorg. Chem., 6 , 463 (1967) ll
P. PAOLETTI, L. FABBRIZZI and R. BARBUCCI, Inorg. Chim. Acta Revs., Z , 43 (1973)