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The photo-induced reaction of Mn 2 (CO) 10  with the olefinic phosphane P(C 7 H 7 )3 (1; [P] if coordinated to a metal) leads stepwise to the axially substituted derivatives ax-{Mn 2 (CO) 9 [P]} (2) and ax,ax-{Mn 2 (CO) 8 [P] 2 } (3). Oxidative cleavage of 3 by halogens gives cis-{Mn(X)(CO) 4 [P]} (X = Cl (4a), Br (4b), I (4c)), whereas oxidation of 3 with NOBF 4  provides a route to the salt {Mn(CO) 4 [P]}BF 4  (5) which is also accessible by halide abstraction from 4b by AgBF 4 . The reactivity of the bromo complex 4b has been studied, and analogues such as cis-{Mn(R)(CO) 4 [P]} (R = Me (4d), Fc (4e) and N( i Pr) 2  (4f)) have been prepared. The displacement of a carbonyl ligand from 4b by iodide leads to mer-{Mn(I)(CO) 3 [P]} (6c) and by 1 to mer,trans-{Mn(Br)(CO) 3 [P] 2 } (7b). The complexes mer-{Mn(X)(CO) 3 [P]} (6a-c) are obtained by splitting the dimers, Mn 2 (CO) 6 (CH 3 CN) 2 - (μ −X) 2  (X = Cl, Br, I), with P(C 7 H 7 ) 3  (1). The cation in 5 and the halogeno compounds 6a-c contain [P] (1) as a chelating four-electron ligand which uses one cyclohepta-2,4,6-trienyl substituent for π-complexation. The coordinated double bond in 6c can be displaced by phosphites P(OR)3 (R = Me, Et) to give fac-{Mn(I)(CO) 3 [P(C 7 H 7 ) 3 ][P(OR) 3 ]} (8c). The structures of the new complexes 2-8 have been assigned on the basis of their carbonyl stretching absorption patterns in the IR spectra and by their NMR spectra ( 1 H,  13 C,  31 P). Single-crystal X-ray structure analyses have been carried out for 3 and 6c.

Dinuclear Derivatives of Mn 2 (CO) 10 with the Ligand Tri(1-Cyclohepta- 2,4,6-Trienyl)Phosphane, P(C 7 H 7 ) 3 , and their Oxidative Cleavage