Coordination chemistry of [CH2(PPh2) (P(Y)R2)] and [CH(PPh2)(P(Y)R2)]−, Y = S or Se, R = Ph or tBu: rhodium, iridium and ruthenium complexes; 13C 31P, and 77 Se NMR studies; and the crystal and molecular structures of [Ir(cod)CH2(PPh2)(P(S)tBu2)-P,S]BF4 · CHCl3, [Rh(cod)CH2(PPh2)(P(S)tBu2)-P,SClO4 · CH2Cl2 [Rh(cod)CH(PPh2) (P(S)Ph2)-P,S] and [RuCl2(p-cymene)CH2(PPh2)(P(S) Ph2) -P] · CH2Cl2
作者:Jane Browning、Gordon W. Bushnell、Keith R. Dixon、Robert W. Hilts
DOI:10.1016/0022-328x(93)83192-x
日期:1993.6
characterized by complete 13C, 31P, and 77Se nuclear magnetic resonance (NMR) studies and by four crystal structure determinations. The complexes [Ir(cod)(CH2(PPh2)(P(S)tBu2)-P,S]BF4·CHCl3 (1), [Rh(cod)(CH2(PPh2)(P(S)tBu2)-P,S]ClO4·CH2Cl2 (2), [Rh(cod)(CH(PPh2)(P(S)Ph2-P,S] (3) and [RuCl2(p-cymene)(CH2(PPh2)(P(S)Ph2)-P]· CH2Cl2 (4) crystallize in the P (No. 2) space group (Z 2) with respective unit cells:
氯桥联配合物[M 2 Cl 2(cod)2 ],MIr或Rh,COD环辛二烯与CH 2(PPh 2)(P(Y)R 2),YS或Se的反应RPh或t Bu,为阳离子[M(cod)(CH 2(PPh 2)(P(Y)R 2)-P,S ] +的合成提供了途径,这些阳离子被分离为氟硼酸根或高氯酸根用氢化钠处理这些产物可轻松地将质子去质子化为[M(cod)CH(PPh 2)(P(Y)Ph 2)-P,S)],当YS时,中性配合物也可以通过[M 2 Cl 2(cod)2 ]与Li [CH(PPh 2)(P(S)R 2)]反应获得。阳离子[M(cod)CH 2(PPh 2)(P(S)t Bu 2)-P,S)] +与其他配体Lg(CO)2,(CN t Bu)2的反应,或双(二苯基膦基)甲烷(dppm),导致鳕鱼置换形成[M(Lg)(CH 2(PPh 2)(P(S)t Bu 2)-P,S ] +。CH