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Journal ArticleDOI

Phosphine complexes of the early metals and the lanthanoids

01 Jan 1991-Pure and Applied Chemistry (International Union of Pure and Applied Chemistry)-Vol. 63, Iss: 6, pp 845-850
TL;DR: The coordination chemistry of the mixed-donor tridentate ligand -N(SiMezCH2PR2)2 with the early transition metals of groups 3 and 4 and the lanthanide elements is presented in this paper.
Abstract: The coordination chemistry of the mixed-donor tridentate ligand -N(SiMezCH2PR2)2 with the early transition metals of groups 3 and 4 and the lanthanide elements will be presented. This ancillary ligand has allowed for the formation of phosphine complexes of these hard elements which has in turn induced new reactivity patterns for hydrocarbyl ligands. The stability and reactivity of metal complexes are a function of both the position of the metal in the periodic table and the nature of the ligands. While the former provides for diverse chemical reactivity, it is

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Journal ArticleDOI
TL;DR: In this article, the lithium salt of the bis-furyl substituted disilazide anion, Li{i] [{i} = N(SiMe2R)2 where R = 2-methylfuryl] has been examined as a ligand transfer reagent for the synthesis of group 2 (magnesium) and group 13 (aluminium) compounds.

6 citations

Book ChapterDOI
01 Jan 2015
TL;DR: The research field surrounding rare earth pincer complexes has reached a stage where a comprehensive review about the reactivity and catalytic behavior of these species is justified as mentioned in this paper, and several types of compounds are discussed, including extremely reactive hydrides, cationic species, and intriguing scandium imido complexes.
Abstract: The research field surrounding rare earth pincer complexes has reached a stage where a comprehensive review about the reactivity and catalytic behavior of these species is justified. In this contribution, we begin with a brief introduction on common strategies for the preparation of rare earth pincer complexes, continuing with a section devoted to the versatile reactivity observed for this class of compound. Thereafter, several types of compounds are discussed, including extremely reactive hydrides, cationic species, and intriguing scandium imido complexes. Finally, the last portion of this chapter sums up the hitherto reported catalytic studies, including discussions on ring-opening polymerization of cyclic esters, polymerization of olefins and hydroamination reactions, as well as several examples of more infrequently encountered catalytic processes.

6 citations

Journal ArticleDOI
TL;DR: In this article , the nonspectator reactivity of a transition metal-bound low-symmetry tricoordinate phosphorus ligand was shown to be a potent hydride donor.
Abstract: Hydride transfer catalysis is shown to be enabled by the nonspectator reactivity of a transition metal-bound low-symmetry tricoordinate phosphorus ligand. Complex 1·[Ru]+, comprising a nontrigonal phosphorus chelate (1, P(N(o-N(2-pyridyl)C6H4)2) and an inert metal fragment ([Ru] = (Me5C5)Ru), reacts with NaBH4 to give a metallohydridophosphorane (1H·[Ru]) by P-H bond formation. Complex 1H·[Ru] is revealed to be a potent hydride donor (ΔG°H-,exp < 41 kcal/mol, ΔG°H-,calc = 38 ± 2 kcal/mol in MeCN). Taken together, the reactivity of the 1·[Ru]+/1H·[Ru] pair comprises a catalytic couple, enabling catalytic hydrodechlorination in which phosphorus is the sole reactive site of hydride transfer.

3 citations

Journal ArticleDOI
TL;DR: The coordination chemistry of the mixed-donor tridentate ligand -N(SiMezCH2PR2)2 with the early transition metals of groups 3 and 4 and the lanthanide elements is presented in this paper.
Abstract: The coordination chemistry of the mixed-donor tridentate ligand -N(SiMezCH2PR2)2 with the early transition metals of groups 3 and 4 and the lanthanide elements will be presented. This ancillary ligand has allowed for the formation of phosphine complexes of these hard elements which has in turn induced new reactivity patterns for hydrocarbyl ligands. The stability and reactivity of metal complexes are a function of both the position of the metal in the periodic table and the nature of the ligands. While the former provides for diverse chemical reactivity, it is
Patent
22 Mar 2002
TL;DR: In this paper, a process for polymerization of addition polymerizable monomers with a catalyst composition comprising a Group 4 or 5 metal bis(silane)amido complex corresponding to the formula (1) where the various substituents are as defined in claim 1.
Abstract: A process for polymerization of addition polymerizable monomers with a catalyst composition comprising a Group 4 or 5 metal bis(silane)amido complex corresponding to the formula (1) where the various substituents are as defined in claim 1.