Mononuclear Platinum(II) and Palladium(II) Dithiolate Complexes as Chelate Metalloligands for Preparation of Heterobimetallic d8-d8 Complexes
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- 作者：Jorge Fornié ; s-Cá ; mer ; Anna M. Masdeu-Bultó ; Carmen Claver ; and Christine J. Cardin
- 刊名：Inorganic Chemistry
- 出版年：1998
- 出版时间：June 1, 1998
- 年：1998
- 卷：37
- 期：11
- 页码：2626 - 2632
- 全文大小：155K
- 年卷期：v.37,no.11(June 1, 1998)
- ISSN：1520-510X
文摘
Palladium-rhodium and platinum-rhodium heterobimetallicbridged dithiolate complexes of general formula[(P-P)M(
ntities/mgr.gif">-S-S)Rh(COD)]ClO4 (COD= 1,5-cyclooctadiene. For M = Pt: P-P =(PPh3)2 and S-S =EDT2-(1,2-ethanedithiolate) (1), PDT2-(1,3-propanedithiolate) (2), andBDT2- (1,4-buthanedithiolate) (3);P-P = dppb(1,4-bis(diphenylphosphino)butane) and S-S =EDT2- (4),PDT2- (5), andBDT2- (6); P-P = dppp(1,3-bis(diphenylphosphino)propane) and S-S =EDT2- (7),PDT2- (8), andBDT2- (9). For M = Pd:P-P = dppband S-S = EDT2- (10),PDT2- (11), andBDT2- (12); P-P = dppp andS-S = EDT2- (13),PDT2- (14), andBDT2- (15)) have been prepared.The crystal structures for complexes 1-3,6, 9, and 12 have beendetermined,and hinged structures were found with angles between local coordinationplanes MS2Rh ranging from 111.27ntities/deg.gif">for complex 1 to 151.34ntities/deg.gif"> for complex 3.Metal-metal distances show nonbonding interactions betweenmetals.X-ray data for 1: triclinic, Pntities/onemacr.gif">,a = 11.311(6) Å, b = 12.991(6) Å,c = 16.140(6) Å, 
= 84.86(6)ntities/deg.gif">, 
=75.73(6)ntities/deg.gif">,
= 86.43(6)ntities/deg.gif">, Z = 2, R = 0.0427(Rw = 0.1151). X-ray data for2: triclinic, Pntities/onemacr.gif">, a =11.084(5) Å, b = 13.094(6)Å, c = 16.338(6) Å, = 86.06(6)ntities/deg.gif">, = 75.67(6)ntities/deg.gif">, = 88.55(6)ntities/deg.gif">, Z = 2,R = 0.0470 (Rw = 0.1264).X-ray datafor 3: orthorhombic, Pbca, a =14.439(6) Å, b = 19.807(6) Å, c =38.156(6) Å, Z = 8, R = 0.0864(Rw =0.2457). X-ray data for 6: monoclinic,P21/c, a =20.338(6) Å, b = 14.227(6) Å, c =14.570(6) Å, = 100.94(6)ntities/deg.gif">,Z = 4, R = 0.0536 (Rw= 0.1449). X-ray data for 9: monoclinic,P21/c, a =20.326(6) Å, b = 14.109(6) Å,c= 14.368(6) Å, = 100.90(6)ntities/deg.gif">, Z = 4,R = 0.0380 (Rw = 0.0990).X-ray data for 12: monoclinic,P21/c, a =20.365(6) Å, b = 14.186(6) Å, c =14.592(6) Å, = 101.04(6)ntities/deg.gif">, Z = 4,R = 0.0507 (Rw =0.1500).
ntities/mgr.gif">-S-S)Rh(COD)]ClO4 (COD= 1,5-cyclooctadiene. For M = Pt: P-P =(PPh3)2 and S-S =EDT2-(1,2-ethanedithiolate) (1), PDT2-(1,3-propanedithiolate) (2), andBDT2- (1,4-buthanedithiolate) (3);P-P = dppb(1,4-bis(diphenylphosphino)butane) and S-S =EDT2- (4),PDT2- (5), andBDT2- (6); P-P = dppp(1,3-bis(diphenylphosphino)propane) and S-S =EDT2- (7),PDT2- (8), andBDT2- (9). For M = Pd:P-P = dppband S-S = EDT2- (10),PDT2- (11), andBDT2- (12); P-P = dppp andS-S = EDT2- (13),PDT2- (14), andBDT2- (15)) have been prepared.The crystal structures for complexes 1-3,6, 9, and 12 have beendetermined,and hinged structures were found with angles between local coordinationplanes MS2Rh ranging from 111.27ntities/deg.gif">for complex 1 to 151.34ntities/deg.gif"> for complex 3.Metal-metal distances show nonbonding interactions betweenmetals.X-ray data for 1: triclinic, Pntities/onemacr.gif">,a = 11.311(6) Å, b = 12.991(6) Å,c = 16.140(6) Å, = 84.86(6)ntities/deg.gif">, =75.73(6)ntities/deg.gif">, = 86.43(6)ntities/deg.gif">, Z = 2, R = 0.0427(Rw = 0.1151). X-ray data for2: triclinic, Pntities/onemacr.gif">, a =11.084(5) Å, b = 13.094(6)Å, c = 16.338(6) Å, = 86.06(6)ntities/deg.gif">, = 75.67(6)ntities/deg.gif">, = 88.55(6)ntities/deg.gif">, Z = 2,R = 0.0470 (Rw = 0.1264).X-ray datafor 3: orthorhombic, Pbca, a =14.439(6) Å, b = 19.807(6) Å, c =38.156(6) Å, Z = 8, R = 0.0864(Rw =0.2457). X-ray data for 6: monoclinic,P21/c, a =20.338(6) Å, b = 14.227(6) Å, c =14.570(6) Å, = 100.94(6)ntities/deg.gif">,Z = 4, R = 0.0536 (Rw= 0.1449). X-ray data for 9: monoclinic,P21/c, a =20.326(6) Å, b = 14.109(6) Å,c= 14.368(6) Å, = 100.90(6)ntities/deg.gif">, Z = 4,R = 0.0380 (Rw = 0.0990).X-ray data for 12: monoclinic,P21/c, a =20.365(6) Å, b = 14.186(6) Å, c =14.592(6) Å, = 101.04(6)ntities/deg.gif">, Z = 4,R = 0.0507 (Rw =0.1500).