Synthesis and structures of diphosphinoamide complexes of nickel, palladium and platinum

Musa Said; David L. Hughes; Manfred Bochmann

doi:10.1016/j.poly.2005.07.027

Synthesis and structures of diphosphinoamide complexes of nickel, palladium and platinum

Musa Said, David L. Hughes, Manfred Bochmann

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Abstract

Lithium bis(diphenylphosphino)amide, (THF)₃LiN(PPh₂)₂ reacts with Ni(COD)₂ or PtMe₂(COD) to give the corresponding bimetallic complexes (THF)₃LiN(PPh₂)₂Ni(COD) and (THF)₃LiN(PPh₂)₂PtMe₂. Reaction of (THF)₃LiN(PPh₂)₂Ni(COD) with Me₃SnCl gave the Ni–Sn derivative, also accessible from Me₃SnN(PPh₂)₂. The silyl derivatives Me₃SiN(PPh₂)₂M [M = Ni(COD), PtMe₂] were obtained similarly as red and colourless crystals, respectively. By contrast, the reaction with PdCl₂(COD) afforded an insoluble yellow adduct which, on attempted recrystallisation afforded a small amount of a Pd(I) product, [PdCl{HN(PPh₂)₂}]₂. The crystal structures of the Ni and Pt complexes are based on MP₂N four-membered rings. The geometric parameters proved rather insensitive to changes in the N-main group element bond. In all cases the amido-nitrogen atom deviated slightly from trigonal-planar geometry, most probably as the consequence of packing forces.

Original language	English
Pages (from-to)	843-852
Number of pages	10
Journal	Polyhedron
Volume	25
Issue number	4
DOIs	https://doi.org/10.1016/j.poly.2005.07.027
Publication status	Published - 29 Aug 2005

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@article{f70c4e2834d746888cadc81f0a60422d,

title = "Synthesis and structures of diphosphinoamide complexes of nickel, palladium and platinum",

abstract = "Lithium bis(diphenylphosphino)amide, (THF)3LiN(PPh2)2 reacts with Ni(COD)2 or PtMe2(COD) to give the corresponding bimetallic complexes (THF)3LiN(PPh2)2Ni(COD) and (THF)3LiN(PPh2)2PtMe2. Reaction of (THF)3LiN(PPh2)2Ni(COD) with Me3SnCl gave the Ni–Sn derivative, also accessible from Me3SnN(PPh2)2. The silyl derivatives Me3SiN(PPh2)2M [M = Ni(COD), PtMe2] were obtained similarly as red and colourless crystals, respectively. By contrast, the reaction with PdCl2(COD) afforded an insoluble yellow adduct which, on attempted recrystallisation afforded a small amount of a Pd(I) product, [PdCl{HN(PPh2)2}]2. The crystal structures of the Ni and Pt complexes are based on MP2N four-membered rings. The geometric parameters proved rather insensitive to changes in the N-main group element bond. In all cases the amido-nitrogen atom deviated slightly from trigonal-planar geometry, most probably as the consequence of packing forces.",

author = "Musa Said and Hughes, {David L.} and Manfred Bochmann",

year = "2005",

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doi = "10.1016/j.poly.2005.07.027",

language = "English",

volume = "25",

pages = "843--852",

journal = "Polyhedron",

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T1 - Synthesis and structures of diphosphinoamide complexes of nickel, palladium and platinum

AU - Said, Musa

AU - Hughes, David L.

AU - Bochmann, Manfred

PY - 2005/8/29

Y1 - 2005/8/29

N2 - Lithium bis(diphenylphosphino)amide, (THF)3LiN(PPh2)2 reacts with Ni(COD)2 or PtMe2(COD) to give the corresponding bimetallic complexes (THF)3LiN(PPh2)2Ni(COD) and (THF)3LiN(PPh2)2PtMe2. Reaction of (THF)3LiN(PPh2)2Ni(COD) with Me3SnCl gave the Ni–Sn derivative, also accessible from Me3SnN(PPh2)2. The silyl derivatives Me3SiN(PPh2)2M [M = Ni(COD), PtMe2] were obtained similarly as red and colourless crystals, respectively. By contrast, the reaction with PdCl2(COD) afforded an insoluble yellow adduct which, on attempted recrystallisation afforded a small amount of a Pd(I) product, [PdCl{HN(PPh2)2}]2. The crystal structures of the Ni and Pt complexes are based on MP2N four-membered rings. The geometric parameters proved rather insensitive to changes in the N-main group element bond. In all cases the amido-nitrogen atom deviated slightly from trigonal-planar geometry, most probably as the consequence of packing forces.

AB - Lithium bis(diphenylphosphino)amide, (THF)3LiN(PPh2)2 reacts with Ni(COD)2 or PtMe2(COD) to give the corresponding bimetallic complexes (THF)3LiN(PPh2)2Ni(COD) and (THF)3LiN(PPh2)2PtMe2. Reaction of (THF)3LiN(PPh2)2Ni(COD) with Me3SnCl gave the Ni–Sn derivative, also accessible from Me3SnN(PPh2)2. The silyl derivatives Me3SiN(PPh2)2M [M = Ni(COD), PtMe2] were obtained similarly as red and colourless crystals, respectively. By contrast, the reaction with PdCl2(COD) afforded an insoluble yellow adduct which, on attempted recrystallisation afforded a small amount of a Pd(I) product, [PdCl{HN(PPh2)2}]2. The crystal structures of the Ni and Pt complexes are based on MP2N four-membered rings. The geometric parameters proved rather insensitive to changes in the N-main group element bond. In all cases the amido-nitrogen atom deviated slightly from trigonal-planar geometry, most probably as the consequence of packing forces.

U2 - 10.1016/j.poly.2005.07.027

DO - 10.1016/j.poly.2005.07.027

M3 - Article

VL - 25

SP - 843

EP - 852

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

IS - 4

ER -