Complexes having platinum to metal dative bonds

具有铂与金属配位键的配合物

• 批准号: 12640531
• 负责人: YAMAGUCHI Tadashi
• 金额: $ 2.3万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640531/
• 关键词: metal-metal dative bond; platinum complexes; platinum-silver bond; platinum-rhodium bond; cluster complexes

It has been shown that the occupied d_<z^2> orbital of a d^8 transition metal ion with square-planar coordination geometry can act as a potential donor to another metal ion (M) resulting in a dative M(d^8)→M bond. In this study we synthesize complexes having short unsupported Pt(II)→M dative bonds by using platinum(II) complexes with carbon σ-donor ligands which exert a strong ligand field.(1) From a mixture of [Pt(phpy)_2] (Hphpy = phenylpyridine) and AgClO_4 in acetone, a helical chain complex, [{Pt(phpy)_2}2{Ag(acetone)}2]_n(ClO_4)_<2n>・acetone_n, was obtained, which consists of alternate stacking of [Pt(phpy)_2] and Ag(acetone)^+ connected by platinum to silver dative bond and has large diameter (2.3 nm) of helix.(2) When the silver source contains a a relatively coordinative NO_3^-, tetranuclear Pt_2Ag_2 the rhombus cluster complex [{Pt(phpy)_2}2{Ag(NO_3)}2]・CH_3CN was obtained. The cluster core has a 4-center 2-electron bond that includes not only the platinum to silver dative bonds but also a silver-silver bond.(3) When the rhodium dimer [Rh_2(CF_3COO)_4] was used as an acceptor, the tetranuclear Pt→Rh_2←Pt complex [{Rh_2(CF_3COO)_4}{Pt(phpy)_2}2] was obtained in which the platinum complexes coordinate to axial sites of rhodium dimer. The cluster has both platinum to silver dative bonds and a rhodium-rhodium single bond.These results show not only that platinum complexes in a strong ligand field can make a strong platinum to metal dative bond, but also that the metal-metal dative bond is useful for making large cluster complexes.

结果表明，具有方平面配位几何的d^8过渡金属离子占据的d_<z^2>轨道可以作为另一个金属离子(M)的潜在供体，从而形成与M（d^8）→M键。本研究利用铂（II）配合物与碳σ-给体配合，合成了具有短无负载Pt（II）→M键的配合物。(1)以[Pt(phpy)_2] （Hphpy =苯基吡啶）和AgClO_4在丙酮中的混合物为原料，得到了[{Pt(phpy)_2}2{Ag（丙酮）}2]_n(ClO_4)_<2n>·acetone_n螺旋链配合物，该配合物由[Pt(phpy)_2]和Ag（丙酮）^+由铂与银的共轭键连接而成，螺旋直径大（2.3 nm）。(2)当银源中含有一个相对配位的NO_3^-，四核Pt_2Ag_2时，得到了菱形团簇配合物[{Pt(phpy)_2}2{Ag(NO_3)}2]·CH_3CN。簇核有一个4中心2电子键，它不仅包括铂与银的结合键，还包括银-银键。(3)以铑二聚体[Rh_2(CF_3COO)_4]为受体，得到铂配合物与铑二聚体轴位配位的四核Pt→Rh_2←Pt配合物[{Rh_2(CF_3COO)_4}{Pt(phpy)_2}2]。该簇具有铂与银的结合键和铑-铑单键。这些结果表明，铂配合物在强配体场中不仅可以形成强铂-金属键，而且这种金属-金属键对于形成大簇状配合物是有用的。

项目成果

Tadashi.Yamaguchi: "Triangular Platinum(II) Cluster Complexes and Cluster Core Transformation from Square-planar to Triangular Type"Bull.Chem.Soc.Jpn.. 73. 775-784 (2000)

Tadashi.Yamaguchi：“三角形铂(II)簇络合物和簇核从方形平面到三角形的转变”Bull.Chem.Soc.Jpn.. 73. 775-784 (2000)

Tadashi.Yamaguchi: "A Helical Metal-Metal Bonded Chain via Pt→Ag Dative Bond"J.Am.Chem.Soc.. 123. 743-744 (2001)

Tadashi.Yamaguchi：“通过 Pt→Ag 配位键形成的螺旋金属-金属键合链”J.Am.Chem.Soc.. 123. 743-744 (2001)

Tadashi Yamaguchi, Fumie Yamazaki, Tasuku Ito: "A cyclic tetramer of [Ag(1,4,7-trithiacyclononane)]^+, cyclo-tetrakis(μ-1,4,7-trithiacyclononane-k^3S^4,S^7:kS^1)-tetrasilver(I) tetrakis(trifluoromethanesulfonate)nitromethane disolvate"Acta Crystallogra.Se

Tadashi Yamaguchi、Fumie Yamazaki、Tasuku Ito：“[Ag(1,4,7-trithiacyclononane)]^+ 的环状四聚体，cyclo-tetrakis(μ-1,4,7-trithiacyclononane-k^3S^4,S ^7:kS^1)-四银(I)四(三氟甲磺酸)硝基甲烷二溶剂合物“Acta Crystallogra.Se

Tadashi.Yamaguchi, Fumie Yamazaki, Tasuku Ito: "A Helical Metal-Metal Bonded Chain via Pt→Ag Dative Bond"J. Am. Chem. Soc.. 123. 743-744 (2001)

Tadashi.Yamaguchi、Fumie Yamazaki、Tasuku Ito：“通过 Pt→Ag 配位键的螺旋金属-金属键合链”J. Soc. 123. 743-744 (2001)

Tadashi Yamaguchi, Tasuku Ito: "Tetra-and Trinuclear Platinum(II) Cluster Complexes"Adv. lnorg. Chem.. 52. 205-248 (2001)

Tadashi Yamaguchi、Tasuku Ito：“四核和三核铂（II）簇配合物”Adv.