Molybdenum(0) and tungsten(0) adducts of some bicyclic aminophosphanes having a phosphorus-nitrogen bond in a constrained structure

Febvay, J.; Grec, Dominique; Riess, Jean G.

doi:10.1021/ic50226a050

Cited by 9 publications

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“…When for example the frequency of the v(C0) vibrations of M(CO),L adducts are measured-a commonly used approach to probe the a-accepting ability of a ligand L-one observes that these frequencies are significantly higher than L = 1 than with related but acyclic phosphorus ligands reputed to be strongly Ir-acid (Scheme 17). [22][23][24][25][26][27][28]29 This again is in line with the p,-d, rationale: the overlap of the orbitals concerned being expected to be less effective when nitrogen is pyramidal, the a-acid character of the phosphorus with respect to the metal should be enhanced; but the strain imposed on the angles at phosphorus is also expected to influence this character.…”

Section: Effects Of the Nitrogen Atom On The Donor Character Of The Psupporting

confidence: 57%

About the Coordination Chemistry of the Phosphorus-Nitrogen Entity

Riess

1986

Phosphorous and Sulfur and the Related Elements

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Triply coordinated trivalent nitrogen atoms are known to lose most or all of their Lewis donor capacity when bonded to a third or higher row element. It is shown here, in the case of P-bonded nitrogen atoms, that structural constraints which maintain the nitrogen atom in a pyramidal configuration can contribute much in preserving their basicity and/or nucleophilic character. In particular, nitrogen atoms apically bonded to 5-coordinated formally penta-or trivalent phosphorus atoms can display definite basicity. Examples of metal-and base-induced opening and closing of P-N bonds are also presented. The following unusual coordination modes and/or reaction issues are exemplified:where A can be-depending on the case-H+,CH~,BH,,BF, or a transition metal moiety, as for example CpMo(CO),CI or CpMo(CO),, etc. The factors that affect the rather variable P-N bond length are discussed.

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