Nickel(II) and nickel(0) derivatives of bis(diphenylphosphino)amine: [N(PPh2)2]2Ni, (Ph3P)2Ni[(Ph2P)2NH]. Synthesis, characterization, and some properties

Sushev, Vyacheslav V.; Kornev, A. N.; Fedotova, Yana V.; Kursky, Yurii A.; Mushtina, T. G.; Abakumov, G. A.; Zakharov, Lev N.; Rheingold, Arnold L.

doi:10.1016/s0022-328x(03)00314-0

Cited by 17 publications

(2 citation statements)

References 7 publications

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“…However, the obtained product was only characterized spectroscopically. Kornev and co‐workers published a Ni II complex [Ni(κ 2 ‐ P , P ‐Ph 2 P‐N‐PPh 2 ) 2 ] containing two PNP moieties coordinated at a single metal center by disproportionation of [(Ph 3 P) 2 NiN(SiMe 3 ) 2 ] in the presence of Ph 2 P‐N(H)‐PPh 2 along with the formation of [(Ph 3 P) 2 Ni{η 2 ‐Ph 2 P‐N(H)‐PPh 2 }] 19. The platinum and iron complexes [{η 2 ‐Ph 2 PNP(Ph 2 )NPPh 2 }M(κ 2 ‐ P , P ‐Ph 2 P‐N‐PPh 2 ) 2 ] (M=Fe, Pt) reported by Ellermann et al.…”

Section: Introductionmentioning

confidence: 99%

Highly Strained Heterometallacycles of Group 4 Metallocenes with Bis(diphenylphosphino)amide Ligands

Haehnel

Hansen

Spannenberg

et al. 2012

Chemistry A European J

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A study regarding coordination chemistry of the bis(diphenylphosphino)amide ligand Ph2P‐N‐PPh2 at Group 4 metallocenes is presented herein. Coordination of N,N‐bis(diphenylphosphino)amine (1) to [(Cp2TiCl)2] (Cp=η5‐cyclopentadienyl) generated [Cp2Ti(Cl)P(Ph2)N(H)PPh2] (2). The heterometallacyclic complex [Cp2Ti(κ2‐P,P‐Ph2P‐N‐PPh2)] (3 Ti) can be prepared by reaction of 2 with n‐butyllithium as well as from the reaction of the known titanocene–alkyne complex [Cp2Ti(η2‐Me3SiC2SiMe3)] with the amine 1. Reactions of the lithium amide [(thf)3Li{N(PPh2)2}] with [Cp2MCl2] (M=Zr, Hf) yielded the corresponding zirconocene and hafnocene complexes [Cp2M(Cl){κ2‐N,P‐N(PPh2)2}] (4 Zr and 4 Hf). Reduction of 4 Zr with magnesium gave the highly strained heterometallacycle [Cp2Zr(κ2‐P,P‐Ph2P‐N‐PPh2)] (3 Zr). Complexes 2, 3 Ti, 4 Hf, and 3 Zr were characterized by X‐ray crystallography. The structures and bondings of all complexes were investigated by DFT calculations.

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Section: Introductionmentioning

confidence: 99%

Highly Strained Heterometallacycles of Group 4 Metallocenes with Bis(diphenylphosphino)amide Ligands

Haehnel

Hansen

Spannenberg

et al. 2012

Chemistry A European J

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“…In this contribution we extend the scope of our synthetic methodology, reporting the synthesis, isolation, and structural characterization of new alkoxo and amido complexes of nickel of the type Ni(Me)(OR)(dippe) and Ni(Me)(NRR‘)(dippe) (R, R‘ = alkyl). The latter are highly unusual compounds since most of the available examples of group 10 amido complexes are currently limited to arylamides, 3c, silylamides, and the parent amidonickel complex (PCP iPr )Ni-NH 2 4a (PCP iPr = C 6 H 3 -2,6-(CH 2 P i Pr 2 ) 2 ). In addition, we explore the reactivity of those complexes toward heterocumulenes (CO 2 , PhNCO, and PhNCS), a reaction that has been used as a probe to gauge the nucleophilicity of metal alkoxo and amido complexes. 1d,6a, …”

Section: Introductionmentioning

confidence: 99%

Monomeric Alkoxo and Amido Methylnickel(II) Complexes. Synthesis and Heterocumulene Insertion Chemistry

et al. 2007

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Fluoride displacement from the complex Ni(Me)(F)(dippe) by LiOR or LiNRR′ provides an efficient method for the synthesis of the corresponding mononuclear Ni(II) alkoxo or amido complexes. These complexes undergo addition reactions to heterocumulenes (CO 2 , PhNCO, PhNCS), leading to the formal insertion of these molecules into the Ni-O or Ni-N bonds. The dialkylamido complexes decompose through β-hydrogen elimination processes, which selectively afford η 2 -imine Ni(0) compounds.

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Phosphorus–Nitrogen CompoundsBased in part on the article Phosphorus–Nitrogen Compounds by Robert H. Neilson which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Haiduc

2005

Encyclopedia of Inorganic Chemistry

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Phosphorus displays several oxidation states (+II, +III , +IV, and +V ) and coordination numbers (from one to six), and with nitrogen (also two‐, three‐, and four‐coordinate) can form a broad variety of compounds (purely inorganic or organo‐ N ‐ or ‐ P ‐substituted). In addition to mononuclear PN compounds, many short‐chain, polymeric, and cyclic compounds based on molecular skeletons formed by PN alternation are known. There are numerous classes of phosphorus–nitrogen compounds, and this article makes an attempt to introduce the most important ones in the limited space available by selecting what seem to be the most illustrative examples from a very rich chapter of chemistry.

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Nickel(II) and nickel(0) derivatives of bis(diphenylphosphino)amine: [N(PPh2)2]2Ni, (Ph3P)2Ni[(Ph2P)2NH]. Synthesis, characterization, and some properties

Cited by 17 publications

References 7 publications

Highly Strained Heterometallacycles of Group 4 Metallocenes with Bis(diphenylphosphino)amide Ligands

Highly Strained Heterometallacycles of Group 4 Metallocenes with Bis(diphenylphosphino)amide Ligands

Monomeric Alkoxo and Amido Methylnickel(II) Complexes. Synthesis and Heterocumulene Insertion Chemistry

Phosphorus–Nitrogen CompoundsBased in part on the article Phosphorus–Nitrogen Compounds by Robert H. Neilson which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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