Reactivity of (Ferrocenylmethyl)phosphine toward Palladium and Platinum Chlorides. X-ray Structure of [Pd(PH2CH2Fc)Cl(
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- 作者：Maria Michela Dell'Anna ; Ulli Englert ; Mario Latronico ; Pablo Lorenzo Luis ; Piero Mastrorilli ; Daniela Giardina Papa ; Cosimo Francesco Nobile ; Maurizio Peruzzini
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：August 21, 2006
- 年：2006
- 卷：45
- 期：17
- 页码：6892 - 6900
- 全文大小：164K
- 年卷期：v.45,no.17(August 21, 2006)
- ISSN：1520-510X
文摘
The reaction of 2 equiv of the air-stable primary phosphine (ferrocenylmethyl)phosphine (PH2CH2Fc, 1) with [Pd(cod)Cl2] (Fc = ferrocenyl; cod = 1,5-cyclooctadiene) at 298 K gave the phosphanido-bridged Pd(II) tetramer[Pd(PH2CH2Fc)Cl(
-PHCH2Fc)]4 (2), which shows an unprecedented arrangement of four Pd atoms embedded inan eight-membered Pd4P4 ring. An X-ray diffraction study showed that 2 crystallizes in the triclinic space group P
with a = 17.607(7) Å, b = 17.944(7) Å, c = 18.792(7) Å, 
= 107.120(12)
, 
= 96.344(13), 
= 117.087(15).Each molecule contains four palladium atoms in a distorted square-planar coordination formed by one chlorine andthree phosphorus atoms. Two of the latter belong to bridging primary phosphanides and the remaining one iscontributed by a terminal PH2CH2Fc ligand. The coordination environments of neighboring metal centers adopt analmost perpendicular mutual orientation. The reaction of 2 equiv of 1 with [Pt(cod)Cl2] at 323 K yielded the analogousPt(II) tetramer of formula [Pt(PH2CH2Fc)Cl(-PHCH2Fc)]4 (3), which was fully characterized by multinuclear anddynamic NMR, IR, and elemental analyses. Single-crystal X-ray diffraction on 3 confirmed the tetranuclear arrangementin the solid state, but orientational disorder of the molecule precludes a more detailed discussion of the structure.Low-temperature NMR experiments in CD2Cl2 showed the presence of two slowly interconnecting conformers.Reaction of 1 and [M(cod)Cl2] (M = Pd or Pt) at lower temperatures (273 K for Pd, 295 K for Pt) in dichloromethaneallowed the detection in solution of the mononuclear species cis-[M(PH2CH2Fc)2Cl2] (M = Pd, 4; M = Pt, 5) which,upon heating, transformed into the tetramers 2 and 3, respectively. Solid samples of 4 and 5 could be isolatedafter workup at low temperature and were characterized by conventional spectroscopic methods.
-PHCH2Fc)]4 (2), which shows an unprecedented arrangement of four Pd atoms embedded inan eight-membered Pd4P4 ring. An X-ray diffraction study showed that 2 crystallizes in the triclinic space group Pwith a = 17.607(7) Å, b = 17.944(7) Å, c = 18.792(7) Å, = 107.120(12), = 96.344(13), = 117.087(15).Each molecule contains four palladium atoms in a distorted square-planar coordination formed by one chlorine andthree phosphorus atoms. Two of the latter belong to bridging primary phosphanides and the remaining one iscontributed by a terminal PH2CH2Fc ligand. The coordination environments of neighboring metal centers adopt analmost perpendicular mutual orientation. The reaction of 2 equiv of 1 with [Pt(cod)Cl2] at 323 K yielded the analogousPt(II) tetramer of formula [Pt(PH2CH2Fc)Cl(-PHCH2Fc)]4 (3), which was fully characterized by multinuclear anddynamic NMR, IR, and elemental analyses. Single-crystal X-ray diffraction on 3 confirmed the tetranuclear arrangementin the solid state, but orientational disorder of the molecule precludes a more detailed discussion of the structure.Low-temperature NMR experiments in CD2Cl2 showed the presence of two slowly interconnecting conformers.Reaction of 1 and [M(cod)Cl2] (M = Pd or Pt) at lower temperatures (273 K for Pd, 295 K for Pt) in dichloromethaneallowed the detection in solution of the mononuclear species cis-[M(PH2CH2Fc)2Cl2] (M = Pd, 4; M = Pt, 5) which,upon heating, transformed into the tetramers 2 and 3, respectively. Solid samples of 4 and 5 could be isolatedafter workup at low temperature and were characterized by conventional spectroscopic methods.