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)OPPh2}] and [Mo3(μ3-I)2{μ2-Ph2P(CH2)PPh2}3]I

Equimolar quantities of [MoI2(CO)(3) (Ph2P(CH2)(n)PPh2}] (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)(n)PPh2}][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)(3)L{Ph2P(CH2)PPh2}][BF4], {L = NCEt 4, P(OMe)(3) 5, P(OEt)(3) 6} or [MoI(CO)(2)(NCMe)L(Ph2P(CH2)(n)PPh2}][BF4] {L = P(OPri)(3) 7, P(OPh)(3) 8, PPh3 9}. 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-Me-2- 1, 10-phen, 2,2'-bipy, Ph2P(CH2)(n)PPh2 (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)(2)PPh2 give the complexes, [MoI(CO)(2){Ph2P(CH2)PPh2} {Ph2P(CH2)(n)PPh2}][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 = NMe2 19, NEt2 20, NC4H8 21). 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 [Mo-3(mu(3)-I)(2) {mu(2)-Ph2P(CH2)PPh2}(3)]I, are obtained as decomposition products. (C) 2002 Elsevier Science B.V. All rights reserved.