103817-27-2Relevant academic research and scientific papers
Preparation, properties, and reactions of metal-containing heterocycles. 51. Three- and five-membered phosphacobaltacycloalkanes
Lindner, Ekkehard,Neese, Petra,Hiller, Wolfgang,Fawzi, Riad
, p. 2030 - 2036 (2008/10/08)
The synthesis of three- and five-membered phosphacobaltacycloalkanes (OC)3CoPPh2CH2 (3a), (OC)3CoPPh2(CH2)3 (4a), and (OC)3CoP(C6H11)2(CH 2)3 (4b) by reductive cycloelimination of [(OC)3CoPPh2CH2Cl]2 (1a), [(OC)3CoPPh2(CH2)3Cl]2 (2a), and [(OC)3CoP(C6H11)2(CH 2)3Cl]2 (2b) is described. Reaction of the five-membered ring with CO or PPh3 results either in CO insertion into the metal-alkyl C bond forming (OC)3CoPPh2(CH2)3C=O (5a), (OC)3CoP(C6H11)2(CH 2)3C=O (5b), and Ph3P(OC)2CoPPh2(CH2)3C=O (6a), respectively, or in CO substitution yielding Ph3P(OC)2COP-(C6H11) 2(CH2)3 (7b). The products were characterized by IR, NMR (1H, 13C, and 31P), and mass spectroscopy. Single crystals of (OC)3CoPPh2CH2 (3a) are monoclinic of space group P21/c with a = 10.498 (4) ?, b = 7.697 (3) ?, c = 18.783 (5) ?, β = 98.29 (2)°, and Z = 4. Single crystals of (OC)3CoP(C6H11)2(CH 2)3 (4b) are triclinic of space group P1 with a = 9.999 (5) ?, b = 12.910 (5) ?, c = 8.364 (3) ?, α = 101.81 (3)°, β = 101.28 (3)° γ = 112.44 (4)°, and Z = 2. The cobalt coordination in (OC)3CoPPh2CH2 (3a) is a distorted trigonal bipyramid. According to a short P-C(4) bond of 1.725 (5) ? the Co-P-C ring is described as a phosphorus ylide with a complexed ylidic C(4) atom. (OC)3CoP(C6H11)2(CH 2)3 (4b) is essentially a metallacyclopentane with a trigonal-bipyramidal coordinated cobalt.
