SYNTHESIS OF DIMANGANESE COMPLEXES CONTAINING MIXED BRIDGING PHOSPHIDO LIGANDS - CRYSTAL-STRUCTURES OF [MN-2(MU-PPH(2))(MU-PPHMN(CO)(5))(CO)(8)] AND [MN-2(MU-PPHH)(MU-PPHCOME)(CO)(8)]
L. Manojlovicmuir et al., SYNTHESIS OF DIMANGANESE COMPLEXES CONTAINING MIXED BRIDGING PHOSPHIDO LIGANDS - CRYSTAL-STRUCTURES OF [MN-2(MU-PPH(2))(MU-PPHMN(CO)(5))(CO)(8)] AND [MN-2(MU-PPHH)(MU-PPHCOME)(CO)(8)], Journal of organometallic chemistry, 491(1-2), 1995, pp. 255-262
The synthesis of a number of dimanganese complexes each containing two
different bridging phosphido ligands is reported. The complex [Mn-2(m
u-PPh(2))(mu-PPhH)(CO)(8)] (1) is prepared by the reaction of [Mn-2(CO
)(10)] firstly with PPh(2)H followed by reaction with PPhH(2) in decal
in. The reaction of 1 with CCl4 gives [Mn-2(mu PPh(2))(mu-PPhCl)(CO)(8
)] (2) and deprotonation of 1 with n-BuLi followed by reaction of the
deprotonated species with RX (X = halide) or [Mn(CO),Br] gives the com
plexes [Mn-2(mu-PPh(2))(mu-PPhR)(CO)(8)] (R = Me(3a), Et(3b), CH(2)COM
e(3c) or CO(2)Et(3d)) and [Mn(mu-PPh(2)){mu-PPhMn(CO)(5)}(CO)(8)] (4).
The deprotonation of [Mn-2(mu-PPhH)(2)(CO)(8)] with one equivalent of
n-BuLi and subsequent reaction with MeCOCl gives [Mn-2(mu-PPhH)(mu-PP
hCOMe)(CO)(8)] (5) which exists in solution as a mixture of isomers. T
he structures of [Mn-2(mu-PPh(2)){mu-PPhMn(CO)(5)}(CO)(8)] (4) and of
trans-[Mn-2(mu-PPhH)(mu-PPhCOMe)(CO)(8)] (5) have been determined by s
ingle-crystal X-ray studies. All the complexes have been characterized
spectroscopically and by elemental analysis.