Synthesis and reactions of the cationic seven-coordinate complexes, [MoI(CO)3(NCR){Ph2P(CH2)nPPh2}][BF4] (R=Me, n=1, 2 and 3; R=Et, n=1). Crystal structures of [MoI2(CO)2(PPh3){Ph2P(CH2)PPh2}], [MoI(CO)2{Ph2P(CH2)PPh2}2][BF4]·CH2Cl2, [MoCl3O{Ph2PO(CH2)OPP

Equimolar quantities of [MoI2(CO)3{Ph2P(CH2)nPPh2}] (n=1, 2 or 3) and Ag[BF4] were reacted in acetonitrile at room temperature to give the cationic seven-coordinate complexes, [MoI(CO)3(NCMe){Ph2P(CH2)nPPh2}][BF4], (1–3), in high yield. Reactions of [MoI(CO)3(NCMe){Ph2P(CH2)PPh2}][BF4] (1) with one equivalent of L in CH2Cl2 at room temperature afford either [MoI(CO)3L{Ph2P(CH2)PPh2}][BF4], {L=NCEt 4, P(OMe)35, P(OEt)36} or [MoI(CO)2(NCMe)L{Ph2P(CH2)nPPh2}][BF4] {L=P(OPri)37, P(OPh)38, PPh39}. Complex 9 reacts with NaI to give the crystallographically characterised complex, [MoI2(CO)2(PPh3){Ph2P(CH2)PPh2}] (10). Treatment of 1 with equimolar amounts of L∧L {where L∧L=1,10-phen, 4,7-Me2-1,10-phen, 2,2′-bipy, Ph2P(CH2)nPPh2 (n=1, 2 and 3)} yielded the cationic complexes [MoI(CO)(L∧L){Ph2P(CH2)PPh2}][BF4] (11–16). Complex 14, {L∧L=Ph2P(CH2)PPh2}, has been crystallographically characterised. Equimolar quantities of 2, 3 and Ph2P(CH)2PPh2 give the complexes, [MoI(CO)2{Ph2P(CH2)PPh2}{Ph2P(CH2)nPPh2}][BF4] {n=2, 17, n=3, 18). Reaction of equimolar amounts of 1 and [S2CX]− affords the neutral complexes [MoI(CO)2(S2CX){Ph2P(CH2)PPh2}], (where X=NMe219, NEt220, NC4H821). Reaction of 1 and NaX (X=F, Cl) or KSCN, in equimolar ratio, gave the neutral complexes [MoXI(CO)3{Ph2P(CH2)PPh2}] (22–24) in good yield. Upon exposure to air of concentrated solutions of complex 1 in CDCl3, the unusual crystallographically characterised species, [MoCl3O{Ph2PO(CH2)OPPh2}] and [Mo3(μ3-I)2{μ2-Ph2P(CH2)PPh2}3]I, are obtained as decomposition products.