Molybdenum and Tungsten Cyclopentadienone Complexes. 1. Synthesis and Characterization
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- 作者：Klaus Mauthner ; Christian Slugovc ; Kurt Mereiter ; Roland Schmid ; and Karl Kirchner
- 刊名：Organometallics
- 出版年：1996
- 出版时间：January 9, 1996
- 年：1996
- 卷：15
- 期：1
- 页码：181 - 188
- 全文大小：358K
- 年卷期：v.15,no.1(January 9, 1996)
- ISSN：1520-6041
文摘
The labile complexesM(CO)3(CH3CN)3 (M = Mo,W) undergo facile oxidative additionreactions with 4-bromo-2-cyclopentenone to giveM(
3-C5H5O)(CO)2(CH3CN)2Br1a and 2.Complex 1a crystallizes in space groupP21/m (No. 11) with a =8.631 (2) Å, b = 12.852 (3)Å, c = 6.659 (2) Å, 
= 109.27 (1)
, V= 697.3 (3) Å3, and Z = 2. Thestructure was refinedto R(F) = 0.023 (F 
4
F). 1 and 2 react withpotassium tris(pyrazolyl)borate(K[HBpz3]),2,2'-bipyridyl (bipy), and bis(diphenylphosphino)methane(dppm) to give neutral 3-cyclopentenoyl complexes of typesM(3-C5H5O)(CO)2(HBpz3)3a and 4,M(3-C5H5O)(CO)2(bipy)Br 5 and 6, andM(3-C5H5O)(CO)2(dppm)Br7 and 8, respectively, in high yields.Singlecrystal structural studies have been carried out for complexes3a, 4, and 8. 3acrystallizesin space group Pbca (No. 61) with a = 19.819(3) Å, b = 13.899 (3) Å, c = 13.088 (2) Å,V =3605 (1) Å3, and Z = 8, and the structure wasrefined to R(F) = 0.026 (F 4F). 4 isisostructural with 3a and crystallizes in space groupPbca (No. 61) with a = 19.726 (6) Å,b= 13.924 (6) Å, c = 13.080 (4) Å, V =3593 (2) Å3, and Z = 8, and the structure wasrefinedto R(F) = 0.028 (F 4F). 8 crystallizes in space groupP
(No. 2) with a = 10.143 (3)Å,b = 10.972 (4) Å, c = 13.708 (5) Å, 
=82.52 (2), = 85.07 (2), 
= 84.77 (1),V = 1502.0(9) Å3, and Z = 2. The structure wasrefined to R(F) = 0.029 (F 4F). Treatment ofcomplexes 3-8 withPh3C+PF6- inmethylene chloride solution led to facile hydrideabstraction and formation of the stable cationic4-cyclopentadienone complexes[M(4-C5H4O)(CO)2(HBpz3)]PF6 9a and10,[M(4-C5H4O)(CO)2(bipy)Br]PF611 and 12, and [W(4-C5H4O)(CO)2(dppm)Br]PF6(13). Complex 10 has been found tocrystallize in space groupPcab (No. 61) with a = 18.242 (4) Å,b = 17.145 (4) Å, c = 13.188 (3) Å,V = 4125 (2) Å3, andZ = 8. The structure was refined toR(F) = 0.029 (F 4F). 13 crystallizes in spacegroupP21/n (No. 14) with a =11.796 (3) Å, b = 17.512 (7) Å, c = 17.210(5) Å, = 93.67 (1), V =3548 (2) Å3, and Z = 4. The structurewas refined to R(F) = 0.040 (F 4F).
3-C5H5O)(CO)2(CH3CN)2Br1a and 2.Complex 1a crystallizes in space groupP21/m (No. 11) with a =8.631 (2) Å, b = 12.852 (3)Å, c = 6.659 (2) Å, = 109.27 (1), V= 697.3 (3) Å3, and Z = 2. Thestructure was refinedto R(F) = 0.023 (F 4F). 1 and 2 react withpotassium tris(pyrazolyl)borate(K[HBpz3]),2,2'-bipyridyl (bipy), and bis(diphenylphosphino)methane(dppm) to give neutral 3-cyclopentenoyl complexes of typesM(3-C5H5O)(CO)2(HBpz3)3a and 4,M(3-C5H5O)(CO)2(bipy)Br 5 and 6, andM(3-C5H5O)(CO)2(dppm)Br7 and 8, respectively, in high yields.Singlecrystal structural studies have been carried out for complexes3a, 4, and 8. 3acrystallizesin space group Pbca (No. 61) with a = 19.819(3) Å, b = 13.899 (3) Å, c = 13.088 (2) Å,V =3605 (1) Å3, and Z = 8, and the structure wasrefined to R(F) = 0.026 (F 4F). 4 isisostructural with 3a and crystallizes in space groupPbca (No. 61) with a = 19.726 (6) Å,b= 13.924 (6) Å, c = 13.080 (4) Å, V =3593 (2) Å3, and Z = 8, and the structure wasrefinedto R(F) = 0.028 (F 4F). 8 crystallizes in space groupP (No. 2) with a = 10.143 (3)Å,b = 10.972 (4) Å, c = 13.708 (5) Å, =82.52 (2), = 85.07 (2), = 84.77 (1),V = 1502.0(9) Å3, and Z = 2. The structure wasrefined to R(F) = 0.029 (F 4F). Treatment ofcomplexes 3-8 withPh3C+PF6- inmethylene chloride solution led to facile hydrideabstraction and formation of the stable cationic4-cyclopentadienone complexes[M(4-C5H4O)(CO)2(HBpz3)]PF6 9a and10,[M(4-C5H4O)(CO)2(bipy)Br]PF611 and 12, and [W(4-C5H4O)(CO)2(dppm)Br]PF6(13). Complex 10 has been found tocrystallize in space groupPcab (No. 61) with a = 18.242 (4) Å,b = 17.145 (4) Å, c = 13.188 (3) Å,V = 4125 (2) Å3, andZ = 8. The structure was refined toR(F) = 0.029 (F 4F). 13 crystallizes in spacegroupP21/n (No. 14) with a =11.796 (3) Å, b = 17.512 (7) Å, c = 17.210(5) Å, = 93.67 (1), V =3548 (2) Å3, and Z = 4. The structurewas refined to R(F) = 0.040 (F 4F).