Activation of alkynes by diphosphine- and µ-phosphido-spanned heterobimetallic complexes

Reactivity of heterodinuclear complexes formed by platinum insertion to phosphorus-bridged [1]ferrocenophane coordinating to a metal fragment

The reactivity of the Lewis acid/base stabilized complex of phosphanylalane [(CO)5W(H2PAlH2·NMe3)] (1) towards the Lewis bases THF and NMe3 has been investigated. The reaction with THF leads to decomposition of the complex. One of the decomposition products was identified as containing the anion [{(CO)5W}2PH2]- (2). This anion could be synthesized independently by reaction of [(CO)5WPH3] with KH in the presence of [(CO)5W(THF)] and was isolated as the tetraphenylphosphonium salt [Ph4P][{(CO)5W}2PH2] (2a). The treatment of 1 with NMe3 leads to the formation of [(CO)5W(H2PAlH2·2 NMe3)] (3) containing a five-coordinate aluminum atom. Compound 3 exhibits a fast exchange of the NMe3 ligands in solution containing an excess of NMe3. The products were characterized by spectroscopic methods and X-ray crystallography.

Reactivity of a Phosphanylalane Complex towards Lewis Bases

The carbonylation of a nickel(II) anilido species 2 led to the formation of a dinickel(0)-CO complex (P2 P-PP2 ){Ni(CO)}2 3 with a P-P bond along with isocyanate generation. In this reaction, the central phosphide moiety of an anionic PPP ligand (PPP- =- P[2-Pi Pr2 C6 H4 ]2 ) acts as a single-electron donor to form a P radical. Alternatively, 3 can be synthesized from the reduction of (PPP)NiCl (1) in the presence of CO; thus, the reaction proceeds by radical coupling of a . P-Ni0 -CO species. The reverse reaction occurred to generate 1 when 3 was treated with AgCl. Since the P-P bond is light-sensitive, its homolysis is possible and was explored by EPR spectroscopy and DFT analysis. Finally, various bond-activation reactions of 3 occurred under visible-light conditions, thus indicating that a P-P bond can act as an active reaction site.

A P-P Bond as a Redox Reservoir and an Active Reaction Site.

The synthesis and preliminary coordination chemistry of two new redox-active bidentate ligands containing amido and phosphido donors are described. Treatment of the [RNP]2– (R = Ph, 2,4,6-trimethyl...

Noninnocent Behavior of Bidentate Amidophosphido [NP]2– Ligands upon Coordination to Copper

Phosphido bridged heterodinuclear (Mn/Fe, Mn/Cr, Mn/W) complexes

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Phosphido bridged heterodinuclear (Mn/Fe, Mn/Cr, Mn/W) complexes