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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Reversal of polarization in amidophosphines:neutral-and anionic-kappaP coordination vs.anionic-kappaP,N coordination and the formation of nickelaazaphosphiranes
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Reversal of polarization in amidophosphines:neutral-and anionic-kappaP coordination vs.anionic-kappaP,N coordination and the formation of nickelaazaphosphiranes

机译：氨基膦的极化反转：中性和阴离子-kappaP配位与阴离子-kappaP，N配位和镍基氮杂膦的形成

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Nickel(II)chloride reacts with the bis(tert-butylamino)diazadiphosphetidine {Bu~t(H)NP(mu-NBu~t)_2PN(H)Bu~t} to form trans-[{Bu~t(H)NP(mu-NBu~t)_2PN(H)Bu~t}_2NiCl_2].In solution and the solid-state each heterocyclic ligand coordinates nickel through one phosphorus atom only.For comparison the solid-state structure of the known trans-[NiCl_2(PEt_3)_2] was also determined and it was found that the two complexes have almost identical bond parameters about nickel.The nickel-amidophosphine complexes [{Bu~tOP(mu-NBu~t)_2PNBu~t}NiCl(PBu_3~n)],[(PBu_3~n)ClNi{Bu~tNP(mu-NBu~t)_2PNBu~t}NiCl(PBu_3~n)],and [{Me_2Si(mu-NBu~t)_2PNBu~t}NiCl(PBu_3~n)] were synthesized and X-ray structurally characterized.In these mono-and di-nuclear nickel complexes the nickel ions are coordinated in pseudo square-planar fashions,by one trialkylphosphine ligand,one chloride ligand and one kappaP,N-coordinated amidophosphine moiety from tert-butylamido-substituted heterocycles.Attempts to create nickel complexes chelated in a kappa~2 P fashion by the omicron-phenylenediamine-tethered mono-and di-anionic 1-{Me_2Si(mu-NBu~t)_2PN} 2-{Me_2Si(mu-NBu~t)_2PNH}C_6H_4 and l,2-{Me_2Si(mu-NBu~t)_2PN}C_6H_4,respectively,afforded instead [l,2-{Me_2Si(mu-NBu~t)_2PN}{Me_2Si(mu-NBu~t)_2PN}C_6H_4NiCl] and [l,2-{Me_2Si(mu-NBu~t)_2PN}-{Me_2Si(mu-NBu~t)_2PN}C_6H_4Ni{PEt_3}],each complex having kappaP,N and kappaP coordinated amidophosphine ligands.
机译：氯化镍（II）与双（叔丁基氨基）二氮杂二磷酸{Bu〜t（H）NP（mu-NBu〜t）_2PN（H）Bu〜t}反应形成反式-[{Bu〜t（H） NP（mu-NBu〜t）_2PN（H）Bu〜t} _2NiCl_2]。在溶液和固态中，每个杂环配体仅通过一个磷原子配位镍。为了进行比较，已知反式[[还测定了NiCl_2（PEt_3）_2]，发现这两个配合物的镍键参数几乎相同。镍-氨基膦配合物[{Bu〜tOP（mu-NBu〜t）_2PNBu〜t} NiCl（PBu_3〜 n）]，[（PBu_3〜n）ClNi {Bu〜tNP（mu-NBu〜t）_2PNBu〜t} NiCl（PBu_3〜n）]和[{Me_2Si（mu-NBu〜t）_2PNBu〜t} NiCl （PBu_3〜n）]的合成和X射线结构表征。在这些单核和双核镍配合物中，镍离子以一种伪正方形平面的方式被一个三烷基膦配体，一个氯化物配体和一个κP，N配位。叔胺基取代的杂环的氨基配位的氨基膦部分。试图制造镍络合物螯合物d由the-苯二胺系链的单阴离子和双阴离子1- {Me_2Si（mu-NBu〜t）_2PN} 2- {Me_2Si（mu-NBu〜t）_2PNH} C_6H_4和l ，2- {Me_2Si（mu-NBu〜t）_2PN} C_6H_4分别代替[1,2- {Me_2Si（mu-NBu〜t）_2PN} {Me_2Si（mu-NBu〜t）_2PN} C_6H_4NiCl]和[1，2- {Me_2Si（mu-NBu〜t）_2PN}-{Me_2Si（mu-NBu〜t）_2PN} C_6H_4Ni {PEt_3}]，每个复合物都具有kappaP，N和kappaP配位的氨基膦配体。

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