TY - JOUR
T1 - Synthesis and crystal structures of chloro(trimethylphosphine)tris(trimethylsilylmethyl)molybdenum(IV) and di-μ-chloro-bis[bis(carbonyl)trimethylphosphine(1-2-η- trimethylsilylmethylcarbonyl)molybdenum(II)]
AU - Guzman, Ernesto Carmona
AU - Wilkinson, Geoffrey
AU - Rogers, Robin D.
AU - Hunter, William E.
AU - Zaworotko, Michael J.
AU - Atwood, Jerry L.
PY - 1980
Y1 - 1980
N2 - Tetrachlorobis(tetrahydrofuran)molybdenum and bis(trimethylsilylmethyl)magnesium react in the presence of trimethylphosphine to give a five-co-ordinate molybdenum(IV) alkyl MoCl(CH2SiMe3)3(PMe3), which upon carbonylation at room temperature and pressure yields [MoCl(1-2-η-COCH2SiMe3)(CO)2(PMe 3)]2. l.r. and 1H n.m.r. data for the latter complex suggest the presence of an η2-acyl linkage, a result later confirmed by an X-ray crystal-structure determination. The crystal structures of MoCl(CH2SiMe3)3(PMe3) and [MoCl(COR)(CO)2-(PMe3)]2 have been determined from three-dimensional X-ray diffraction data collected by counter methods. The former crystallizes in the monoclinic space group P21/n with a = 10.400(5), b = 19.029(7), c = 12.849(5) Å, β = 91.74(4)°, and Z = 4 for Dc = 1.23 g cm-3. The final R value was 0.033 for 2 198 independent observed reflections. Electron deficiency at the metal centre of this five-co-ordinate molybdenum compound is the apparent cause of the very short molybdenum-carbon σ-bond length of 2.110(16) Å. [MoCl(COR)(CO)2(PMe3)]2 crystallizes in the monoclinic space group P21/c with a = 8.415(3), b = 10.484(3), c = 19.229(5) Å, β = 90.62(2)°, and Z = 2 for Dc = 1.48 g cm-3. A final R value of 0.020 was obtained based on 2 579 independent observed reflections. The molecule exists as a chlorine-bridged dimer with an η2-acyl linkage. The molybdenum-carbon(acyl) bond length is 2.023(3) Å and the molybdenum-oxygen(acyl) distance is 2.292(2) Å.
AB - Tetrachlorobis(tetrahydrofuran)molybdenum and bis(trimethylsilylmethyl)magnesium react in the presence of trimethylphosphine to give a five-co-ordinate molybdenum(IV) alkyl MoCl(CH2SiMe3)3(PMe3), which upon carbonylation at room temperature and pressure yields [MoCl(1-2-η-COCH2SiMe3)(CO)2(PMe 3)]2. l.r. and 1H n.m.r. data for the latter complex suggest the presence of an η2-acyl linkage, a result later confirmed by an X-ray crystal-structure determination. The crystal structures of MoCl(CH2SiMe3)3(PMe3) and [MoCl(COR)(CO)2-(PMe3)]2 have been determined from three-dimensional X-ray diffraction data collected by counter methods. The former crystallizes in the monoclinic space group P21/n with a = 10.400(5), b = 19.029(7), c = 12.849(5) Å, β = 91.74(4)°, and Z = 4 for Dc = 1.23 g cm-3. The final R value was 0.033 for 2 198 independent observed reflections. Electron deficiency at the metal centre of this five-co-ordinate molybdenum compound is the apparent cause of the very short molybdenum-carbon σ-bond length of 2.110(16) Å. [MoCl(COR)(CO)2(PMe3)]2 crystallizes in the monoclinic space group P21/c with a = 8.415(3), b = 10.484(3), c = 19.229(5) Å, β = 90.62(2)°, and Z = 2 for Dc = 1.48 g cm-3. A final R value of 0.020 was obtained based on 2 579 independent observed reflections. The molecule exists as a chlorine-bridged dimer with an η2-acyl linkage. The molybdenum-carbon(acyl) bond length is 2.023(3) Å and the molybdenum-oxygen(acyl) distance is 2.292(2) Å.
UR - http://www.scopus.com/inward/record.url?scp=37049113492&partnerID=8YFLogxK
U2 - 10.1039/DT9800000229
DO - 10.1039/DT9800000229
M3 - Article
AN - SCOPUS:37049113492
SN - 1472-7773
SP - 229
EP - 234
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 2
ER -