单核铂（II）和钯（II）二硫醇盐配合物作为螯合金属配体用于制备异双核d(8)-d(8)配合物
Mononuclear Platinum(II) and Palladium(II) Dithiolate Complexes as Chelate Metalloligands for Preparation of Heterobimetallic d(8)-d(8) Complexes.
作者信息
Forniés-Cámer Jorge, Masdeu-Bultó Anna M., Claver Carmen, Cardin Christine J.
机构信息
Departament de Química, Universitat Rovira i Virgili, Pl. Imperial Tarraco, 1, 43005 Tarragona, Spain, and Department of Chemistry, The University of Reading, Whiteknights, P.O. Box 224, Reading RG6 6AD, U.K.
出版信息
Inorg Chem. 1998 Jun 1;37(11):2626-2632. doi: 10.1021/ic970557o.
Palladium-rhodium and platinum-rhodium heterobimetallic bridged dithiolate complexes of general formula [(P-P)M(&mgr;-S-S)Rh(COD)]ClO(4) (COD = 1,5-cyclooctadiene. For M = Pt: P-P = (PPh(3))(2) and S-S = EDT(2)(-) (1,2-ethanedithiolate) (1), PDT(2)(-) (1,3-propanedithiolate) (2), and BDT(2)(-) (1,4-buthanedithiolate) (3); P-P = dppb (1,4-bis(diphenylphosphino)butane) and S-S = EDT(2)(-) (4), PDT(2)(-) (5), and BDT(2)(-) (6); P-P = dppp (1,3-bis(diphenylphosphino)propane) and S-S = EDT(2)(-) (7), PDT(2)(-) (8), and BDT(2)(-) (9). For M = Pd: P-P = dppb and S-S = EDT(2)(-) (10), PDT(2)(-) (11), and BDT(2)(-) (12); P-P = dppp and S-S = EDT(2)(-) (13), PDT(2)(-) (14), and BDT(2)(-) (15)) have been prepared. The crystal structures for complexes 1-3, 6, 9, and 12 have been determined, and hinged structures were found with angles between local coordination planes MS(2)Rh ranging from 111.27 degrees for complex 1 to 151.34 degrees for complex 3. Metal-metal distances show nonbonding interactions between metals. X-ray data for 1: triclinic, P&onemacr;, a = 11.311(6) Å, b = 12.991(6) Å, c = 16.140(6) Å, alpha = 84.86(6) degrees, beta = 75.73(6) degrees, gamma = 86.43(6) degrees, Z = 2, R = 0.0427 (R(w) = 0.1151). X-ray data for 2: triclinic, P&onemacr;, a = 11.084(5) Å, b = 13.094(6) Å, c = 16.338(6) Å, alpha = 86.06(6) degrees, beta = 75.67(6) degrees, gamma = 88.55(6) degrees, Z = 2, R = 0.0470 (R(w) = 0.1264). X-ray data for 3: orthorhombic, Pbca, a = 14.439(6) Å, b = 19.807(6) Å, c = 38.156(6) Å, Z = 8, R = 0.0864 (R(w) = 0.2457). X-ray data for 6: monoclinic, P2(1)/c, a = 20.338(6) Å, b = 14.227(6) Å, c = 14.570(6) Å, beta = 100.94(6) degrees, Z = 4, R = 0.0536 (R(w) = 0.1449). X-ray data for 9: monoclinic, P2(1)/c, a = 20.326(6) Å, b = 14.109(6) Å, c = 14.368(6) Å, beta = 100.90(6) degrees, Z = 4, R = 0.0380 (R(w) = 0.0990). X-ray data for 12: monoclinic, P2(1)/c, a = 20.365(6) Å, b = 14.186(6) Å, c = 14.592(6) Å, beta = 101.04(6) degrees, Z = 4, R = 0.0507 (R(w) = 0.1500).
通式为[(P-P)M(μ-S-S)Rh(COD)]ClO₄（COD = 1,5-环辛二烯。对于M = Pt：P-P = (PPh₃)₂且S-S = EDT₂⁻（1,2-乙二硫醇盐）（1）、PDT₂⁻（1,3-丙二硫醇盐）（2）和BDT₂⁻（1,4-丁二硫醇盐）（3）；P-P = dppb（1,4-双（二苯基膦基）丁烷）且S-S = EDT₂⁻（4）、PDT₂⁻（5）和BDT₂⁻（6）；P-P = dppp（1,3-双（二苯基膦基）丙烷）且S-S = EDT₂⁻（7）、PDT₂⁻（8）和BDT₂⁻（9）。对于M = Pd：P-P = dppb且S-S = EDT₂⁻（10）、PDT₂⁻（11）和BDT₂⁻（12）；P-P = dppp且S-S = EDT₂⁻（13）、PDT₂⁻（14）和BDT₂⁻（15））的钯-铑和铂-铑异双金属桥连二硫醇盐配合物已被制备出来。已测定配合物1 - 3、6、9和12的晶体结构，发现为铰链结构，局部配位平面MS₂Rh之间的夹角范围从配合物1的111.27°到配合物3的151.34°。金属-金属距离显示出金属之间的非键相互作用。配合物1的X射线数据：三斜晶系，Pī，a = 11.311(6) Å，b = 12.991(6) Å，c = 16.140(6) Å，α = 84.86(6)°，β = 75.73(6)°，γ = 86.43(6)°，Z = 2，R = 0.0427（R(w) = 0.1151）。配合物2的X射线数据：三斜晶系，Pī，a = 11.084(5) Å，b = 13.094(6) Å，c = 16.338(6) Å，α = 86.06(6)°，β = 75.67(6)°，γ = 88.55(6)°，Z = 2，R = 0.0470（R(w) = 0.1264）。配合物3的X射线数据：正交晶系，Pbca，a = 14.439(6) Å，b = 19.807(6) Å，c = 38.156(6) Å，Z = 8，R = 0.0864（R(w) = 0.2457）。配合物6的X射线数据：单斜晶系，P2(1)/c，a = 20.338(6) Å，b = 14.227(6) Å，c = 14.570(6) Å，β = 100.94(6)°，Z = 4，R = 0.0536（R(w) = 0.1449）。配合物9的X射线数据：单斜晶系，P2(1)/c，a = 20.326(6) Å，b = 14.109(6) Å，c = 14.368(6) Å，β = 100.90(6)°，Z = 4，R = 0.0380（R(w) = 0.0990）。配合物12的X射线数据：单斜晶系，P2(1)/c，a = 20.365(6) Å，b = 14.186(6) Å，c = 14.592(6) Å，β = 101.04(6)°，Z = 4，R = 0.0507（R(w) = 0.1500）。
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