Ja. Casares et al., POLY(2-PYRIDYL)PHOSPHINES, PPY(N)PH(3-N) (N=2,3), AND THEIR P-SUBSTITUTED DERIVATIVES AS TRIPODAL LIGANDS IN MOLYBDENUM(0) CARBONYL-COMPLEXES, Inorganic chemistry, 36(1), 1997, pp. 44-49
The final products of the reactions of either [Mo(CO)(6)] or [Mo(CO)(4
)(NBD)] (NBD = norbornadiene) with PPy(3) (Py = 2-pyridyl) or ZPPy(3)
(Z = 0, S, ClAu, C6F5Au) are fac-[Mo(CO)(3)(Py(3)P-N-3)] or fac-[Mo(CO
)(3)(Py(3)PZ-N-3)], where the ligands act as tridentate N-donors. The
use of ZPPhPy(2) (Z = 0, S) leads to fac-[Mo(CO)(3)(ZPPhPy(2)-Z,N-2)],
the ligands acting as tridentate Z,N-2-donors. The crystal structure
of fac-[Mo(CO)(3)(SPPhPy(2)-S,N-2)] was determined by area detector di
ffractometry and shows that the coordination at molybdenum is essentia
lly octahedral but with trigonal elongation. some tetracarbonyl comple
xes which are intermediates in the formation of the above tricarbonyl
complexes have been isolated (cis-[Mo(CO)(4)(PPy(3)-P)(2)] and cis-[Mo
(CO)(4)(ZPPhPy(2)-Z,N)] (Z = 0, S)) or detected (cis-[Mo(CO)(4)(Py(3)P
-N-2)] and cis-[Mo(CO)(4)(SPPy(3)-S,N)]). The syntheses of the new com
plexes [Au(C6F5)(PRPy(3)-P)] (R = Py or Ph) are also described.