METALLOPHOSPHORANES: CARBONYL SUBSTITUTION REACTIONS AND THE X-RAY CRYSTAL STRUCTURE OF cis-Cat2PMn(CO)4P(OPh)3 (Cat = benzodioxyl)

Article abstract of DOI:10.1016/0022-328X(85)87450-7

Cat2PMn(CO)5 (1, cat = ) is found to undergo carbonyl substitution reactions with phosphorus donors to give the isolable products cat2PMn(CO)4L, where L = cis-PPh3 (2); trans-PPh3 (3); cis-P(OMe)3 (4); and cis-P(OPh)3 (5).No evidence for CO insertion into the pentacoordinate P-Mn bond is observed.The X-ray crystal structure of 5 shows that the crystals are monoclinic, space group P2₁/n.The unit cell parameters are: a 10.523(2), b 25.765(5), c 13.344(2) Angstroem, β 99.11(2) deg, and Z = 4.Full matrix least squares refinement reached R = 0.054 for 3099 observed reflections.The pentacoordinate phosphorus adopts a distorted trigonal bipyramid geometry with the Mn in an equatorial position.Noteworthy is the small equatorial O-P-O angle of 11.1(2) deg.