COORDINATION CHEMISTRY OF FUNCTIONAL PHOS PHINES - CARBONYL AND CARBONYL (NITROSYL) TUNGSTEN DERIVATIVES OF 2-DIPHENYLPHOSPHINOANALINE AND 2-DIPHENYLPHOSPHINOBENZOIC ACID

Replacement of CO by monodentate phosphines PR3 in [W(CO)5Cl]-, follow ed by treatment with Ph2PC6H4X-2 of the resulting anions[W(CO)4(PR3)Cl ]-, afforded the mixed phosphine complexes [W(CO)4(PR3)(Ph2PC6H4X-2)] (PR3 = PMe3, PBu3, PPh2Me and PPh3) 1a-1d (X = NH2) and 2a-2d (X = CO2 H), respectively. [W(CO)4(Pb2PC6H4NH2-2)Cl]- (3), prone to further tra nsformation into [W(CO)4(eta2-Ph2PC6H4NH2-2)] (4) after loss of Cl-, r esulted from initial interaction of [W(CO)5Cl]- with Ph2PC6H4NH2-2. Ex cept for minor quantities of [W(CO)3(NO)(PPh2Me)(Ph2PC6H4CO2H-2)][BF4] (5), no well-defined nitrosyl products were accessible from reactions of tetracarbonyls 1 and 2 with NO+ salts. Such derivatives, viz [W(CO )3(NO)(PR3) (Ph2PC6H4NH2-2)][PF6](6), by rapidly ejecting CO under for mation of the more stable [W(CO)2(NO)(PR3)(eta2-Ph2PC6H4NH2-2)][PF6] ( PR3 = PMe3: 7a; PPh2Me: 7b), )2(NO)(eta1-Ph2PC6H4NH2-2)(eta2-Ph2PC6H4N H2-2)][A] (A = SbF6: 8-SbF6; BF4: 8-BF4) and [W(CO)(NO)(eta1-Ph2PC6H4N H2-2)2][BF4](9), could be synthesized via displacement reactions of lo osely-coordinated ligands (FPF5- and MeCN) by Ph2PC6H4NH2-2 from pre-f ormed nitrosyl species, e.g., [W(CO)(NO)(PR3)(FPF5)] and [W(CO)2 (NO)( MeCN)3]+, respectively. The structure of the complexes [NEt4][W(CO)4(P Ph2Me)Cl], [W(CO)4(PPh2Me)(Ph2PC6H4NH2-2)] (1c), [NEt4]2{[W(CO)4(eta2- Ph2PC6H4NH2-2)]2Cl2) (''4.[NEt4]Cl''), [W(CO)2(NO)(PMe3)(eta2-Ph2PC6H4 NH2-2)][PF6] (7a), [W -Ph2PC6H4NH2-2)(eta2-Ph2PC6H4NH2-2)][SbF6](8-SbF 6, as an addition compound with 0.5Et2O and 0.5CH2Cl2), and [W(CO)(NO) (eta2-Ph2PC6H4NH2-2)2][BF4] (9, containing 1H2O of crystallization) ha ve been determined by single-crystal X-ray diffraction studies.