SYNTHESIS AND STRUCTURE OF THE PHOSPHORUS -BRIDGED TRANSITION-METAL COMPLEXES [FE2(CO)6(PR)6] (R=TBU, IPR), [FE2(CO)4(PIPR)6], [FE2(CO)3CL2(PTBU)5], [CO4(CO)10(PIPR)O], [NI5(CO)10(PIPR)6], AND [IR4(C8H12)4CL2(PPH)4]

(P(t)Bu)3 and (P(i)Pr)3 react with [Fe2(CO)9] to form the dinuclear co mplexes [Fe2(CO)6(PR)6] (R = (t)Bu: 1; (i)Pr: 2). 2 is also formed bes ides [Fe2(CO)4(P(i)Pr)6] (3) in the reaction of [Fe(CO)5] with (P(i)Pr )3. When P(i)Pr(P(t)Bu)2 and P(i)PrCl2 are allowed to react with [Fe2( CO)9] it is possible to isolate [Fe2(CO)3Cl2(P(t)Bu)5] (4). The reacti ons of (P(i)Pr)3 with [Co2(CO)8] and [Ni(CO)4] lead to the tetra- and pentanuclear clusters [Co4(CO)10(P(i)Pr)3] (5), [Ni4(CO)10(P(i)Pr)6] [ 2] and [Ni5(CO)10(P(i)Pr)6] (6). Finally the reaction of [Ir4(C8H12)Cl ]2 with K2(PPh)4 leads to the complex [Ir4(C8H12)4Cl2(PPh)4] (7). The structures of 1-7 were obtained by X-ray single crystal structure anal ysis (1: space group P2(1)/c (Nr. 14), Z = 8, a = 1758.8(16) pm, b = 3 625.6(18) pm, c = 1202.7(7) pm, beta = 90.07(3)-degrees; 2: space grou p P1BAR (Nr.2), Z = 1, a = 880.0(2) pm, b = 932.3(3) pm, c = 1073.7(2) pm, alpha = 79.07(2)-degrees, beta = 86.93(2)-degrees, gamma = 72.23( 2)-degrees; 3: space group Pbca (Nr. 61), Z = 8, a = 952.6(8) pm, b = 1787.6(12) pm, c = 3697.2(30) pm; 4: space group P2(1)/n (Nr. 14), Z = 4, a = 968.0(4) pm, b = 3362.5(15) pm, c = 1051.6(3) pm, beta = 109.7 1(2)-degrees; 5: space group P2(1)/n (Nr. 14), Z = 4, a = 1040.7(5) pm , b = 1686.0(5) pm, c = 1567.7(9) pm, beta = 93.88(4)-degrees; 6: spac e group Pbca (Nr. 61), Z = 8, a = 1904.1(8) pm, b = 1959.9(8) pm, c = 2309.7(9) pm. 7: space group P1BAR (Nr. 2), Z = 2, a = 1374.4(7) pm, b = 1476.0(8) pm, c = 1653.2(9) pm, alpha = 83.87(4)-degrees, beta = 88 .76(4)-degrees, gamma = 88.28(4)-degrees).