The reactions of the anions [Cp-2(CO)(4)Mo-2(mu-PRR ')](-) (R, R ' = H, Ph) towards chloroarsines and chlorophosphines; synthesis of complexes containing both bridging phosphido and arsenido groups
Je. Davies et al., The reactions of the anions [Cp-2(CO)(4)Mo-2(mu-PRR ')](-) (R, R ' = H, Ph) towards chloroarsines and chlorophosphines; synthesis of complexes containing both bridging phosphido and arsenido groups, J CHEM S DA, 11, 2000, pp. 1695-1702
Citations number
53
Categorie Soggetti
Inorganic & Nuclear Chemistry
Journal title
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
Deprotonation of the complexes [Cp-2(CO)(4)Mo-2(mu-(PRR2)-R-1)(mu-H)] (R-1
and R-2=H or Ph; Cp=cyclopentadienyl) in THF yields the related anions [Cp-
2(CO)(4)Mo-2(mu-(PRR2)-R-1)](-). The reactivity of these anions towards Ph2
PCl, (EtO)(2)PCl, Ph2AsCl and Me2AsCl has been investigated. The outcome of
the reactions with chlorophosphines depends on the nature of the substitue
nts on the bridging phosphido ligand. Thus reaction of [Cp-2(CO)(4)Mo-2(mu-
PH2)](-) with Ph2PCl yields [Cp-2(CO)(4)Mo-2{mu-P(H)PPh2}(mu-H)], whereas t
he analogous reaction with [Cp-2(CO)(4)Mo-2(mu-PPhR)](-) yields [Cp-2(CO)(x
)Mo-2(mu-PPh2)(mu-PPhR)] (R=H, x=4; R=Ph, x=2). Thermolysis of [Cp-2(CO)(4)
Mo-2(mu-PPhH)(mu-PPh2)] in toluene yields [Cp-2(CO)(2)Mo-2(mu-PPhH)(mu-PPh2
)] and [Cp-2(CO)(O)Mo-2(mu-PPhH)(mu-PPh2)]. In contrast, the reaction of [C
p-2(CO)(4)Mo-2(mu-(PRR2)-R-1)](-) with chloroarsines is not dependent on th
e nature of the R groups either on the phosphorus or arsenic atoms, yieldin
g [Cp-2(CO)(4)Mo-2(mu-(PRR2)-R-1)(mu-AsR23)] in all cases. These complexes
are the first example of transition metal compounds containing both a bridg
ing phosphido and a bridging arsenido group. The crystal structures of [Cp-
2(CO)(4)Mo-2{mu-P(H)PPh2}(mu-H)], [Cp-2(CO)(4)Mo-2(mu-PPhH){mu-P(OEt)(2)}],
and [Cp-2(CO)(4))Mo-2(mu-PH2)(mu-AsMe2)] are reported.