Platinum(II) 1,5-COD Oxo Complexes
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- 作者：Hui Shan ; Alan James ; and Paul R. Sharp
- 刊名：Inorganic Chemistry
- 出版年：1998
- 出版时间：November 2, 1998
- 年：1998
- 卷：37
- 期：22
- 页码：5727 - 5732
- 全文大小：180K
- 年卷期：v.37,no.22(November 2, 1998)
- ISSN：1520-510X
文摘
Three new types of platinum(II) oxo complexes-[(1,5-COD)Pt(
3-O)(AuL)]2(BF4)2 [1, L = PPh3, PPh2Et, PPh2-i-Pr, P(o-tol)3, P(p-tol)3, P(p-MeOC6H4)3, P(p-CF3C6H4)3], [(1,5-COD)Pt{3-O(AuL)2}2](BF4)2 (2), and [(1,5-COD)4Pt4(3-O)2Cl2]X 2 (3, X = BF4; 3a, X = CF3SO3)-are obtained from oxo/chloro exchange reactions between(1,5-COD)PtCl2 and [(LAu)3(3-O)]BF4. Crystals of 1 (L = PPh3) from CDCl3 are triclinic, P
, with (-100 
C)a = 9.187(4) Å, b = 12.149(3) Å, c = 17.680(6) Å, 
= 99.58(2), 
= 102.86(2), 
= 111.63(2), V =1720(1) Å3, and Z = 1. Crystals of 3a from CH2Cl2/toluene are trigonal, P3121, with a = 11.8878(4) Å, c =29.3193(15) Å, V = 3588.3(3) Å3, and Z = 3. The structure of the cationic portion of 1 shows a planar (COD)Pt(-O)2Pt(COD) unit with slightly out-of-plane LAu+ groups linearly coordinated to the oxo ligands. The structureof the cationic portion of 3a is similar and shows a slightly folded (COD)Pt(-O)2Pt(COD) unit with out-of-plane[(COD)PtCl]+ groups coordinated to the oxo ligands. Solutions of 3 in untreated CH2Cl2 or CD2Cl2 depositcrystals of [(1,5-COD)4Pt4(3-O)2(2-OH)](BF4)3 (4) which are monoclinic, P21/n, with a = 18.624(4) Å, b =14.760(2) Å, c = 15.584(5) Å, = 95.538(12), V = 4264(2) Å3, and Z = 4. The core structure of the cationicportion of 4 shows a tetranuclear platinum cation in which the metal atoms occupy the corners of a distortedtetrahedron and two 3-oxo ligands and one 2-hydroxo ligand bridge the four platinum atoms. Reaction of 1 (L= PPh3) with PPh3 gives OPPh3 and [(Ph3P)3PtAuPPh3]BF4 (5) which is also obtained from (Ph3P)4Pt and Ph3PAuBF4. Crystals of 5 from THF are monoclinic, P21/c, with a = 20.426(6) Å, b = 13.4980(11) Å, c = 24.703(9) Å, = 97.166(15), V = 6758(3) Å3, and Z = 4. The structure of 5 consists of an L3Pt-AuL cation wherethe Au atom is linear 2-coordinate and the Pt atom is distorted square-planar 4-coordinate.
3-O)(AuL)]2(BF4)2 [1, L = PPh3, PPh2Et, PPh2-i-Pr, P(o-tol)3, P(p-tol)3, P(p-MeOC6H4)3, P(p-CF3C6H4)3], [(1,5-COD)Pt{3-O(AuL)2}2](BF4)2 (2), and [(1,5-COD)4Pt4(3-O)2Cl2]X 2 (3, X = BF4; 3a, X = CF3SO3)-are obtained from oxo/chloro exchange reactions between(1,5-COD)PtCl2 and [(LAu)3(3-O)]BF4. Crystals of 1 (L = PPh3) from CDCl3 are triclinic, P, with (-100 C)a = 9.187(4) Å, b = 12.149(3) Å, c = 17.680(6) Å, = 99.58(2), = 102.86(2), = 111.63(2), V =1720(1) Å3, and Z = 1. Crystals of 3a from CH2Cl2/toluene are trigonal, P3121, with a = 11.8878(4) Å, c =29.3193(15) Å, V = 3588.3(3) Å3, and Z = 3. The structure of the cationic portion of 1 shows a planar (COD)Pt(-O)2Pt(COD) unit with slightly out-of-plane LAu+ groups linearly coordinated to the oxo ligands. The structureof the cationic portion of 3a is similar and shows a slightly folded (COD)Pt(-O)2Pt(COD) unit with out-of-plane[(COD)PtCl]+ groups coordinated to the oxo ligands. Solutions of 3 in untreated CH2Cl2 or CD2Cl2 depositcrystals of [(1,5-COD)4Pt4(3-O)2(2-OH)](BF4)3 (4) which are monoclinic, P21/n, with a = 18.624(4) Å, b =14.760(2) Å, c = 15.584(5) Å, = 95.538(12), V = 4264(2) Å3, and Z = 4. The core structure of the cationicportion of 4 shows a tetranuclear platinum cation in which the metal atoms occupy the corners of a distortedtetrahedron and two 3-oxo ligands and one 2-hydroxo ligand bridge the four platinum atoms. Reaction of 1 (L= PPh3) with PPh3 gives OPPh3 and [(Ph3P)3PtAuPPh3]BF4 (5) which is also obtained from (Ph3P)4Pt and Ph3PAuBF4. Crystals of 5 from THF are monoclinic, P21/c, with a = 20.426(6) Å, b = 13.4980(11) Å, c = 24.703(9) Å, = 97.166(15), V = 6758(3) Å3, and Z = 4. The structure of 5 consists of an L3Pt-AuL cation wherethe Au atom is linear 2-coordinate and the Pt atom is distorted square-planar 4-coordinate.