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The reaction of Mn(X)(CO) 5  (X = Cl, Br, I) with 2 equivalents of tri(1-cyclohepta-2,4,6- trienyl)phosphane, P(C 7 H 7 ) 3  ((1); [P] if coordinated to a metal) led stepwise first to cis- {Mn(X)(CO) 4 [P]} (X = Cl (4a), Br (4b), I (4c)) and then to mer,trans-{Mn(X)(CO) 3 [P] 2 } (X = Cl (5a), Br (5b), I (5c)). Nucleophilic displacement of the bromo ligand from (5b) by one-, threeor five-electron ligands gave the pseudohalide complexes mer,trans-{Mn(X)(CO) 3 [P] 2 } (X = NCO (5d) and NCS (5e)), the acetylacetonate derivative Mn(acac)(CO) 2 [P] 2  (6) and the halfsandwich complexes CpMn(CO)2[P] (7) or TpMn(CO) 3  (8). According to the X-ray structure determination of 5e the thiocyanate ligand is N-coordinated.

Synthesis and Reactivity of Bromo-Mer-Tricarbonyl-Trans-Bis[Tri(1-Cyclohepta- 2,4,6-Trienyl)Phosphane]-Manganese, Mnbr(CO) 3 [P(C 7 H 7 ) 3 ] 2