Imidazoline‐Functionalized Diphosphines: Models for N‐Heterocyclic Carbene–Diphosphinocarbene Coupling

Abstract

The next generation: Diphosphinocarbene (Arduengo carbene) and imidazol‐2‐ylidene (Bertrand carbene) are combined in complex 2, which was prepared by reaction of the diphosphinoketenimine complex 1 with propargylamine to form a new type of P2CCN2 electron‐rich olefin, which behaves as a strongly basic diphosphine.

Unexpected Metal-Induced Isomerisms and Phosphoryl Migrations in Pt(II) and Pd(II) Complexes of the Functional Phosphine 2-(Bis(diphenylphosphino)methyl)-oxazoline

“…The three longest P− C bond lengths correspond to species in which CR′ is an alkyl substituent, whereas in the samples showing the three shortest P− C separations, CR′ is a methylene or C CR′ is an allene moiety . An intermediate situation is observed in complex 3b , similar to that found in complexes in which the substituent CR′ contains a delocalized π system (e.g., aromatic imidazole or pyridine, , −C(CO 2 Me)CH(CO 2 Me)). A recent example of a Pd(II) complex bischelated by substituted anionic dppm ligands featured a phosphonate group attached to the P−C−P carbon …”

Phosphorus-ylides: powerful substituents for the stabilization of reactive main group compounds

“…Thus, while offering steric protection through the large phosphonium moiety, donor strengths similar to those of NHCs, which are usually considered to be stronger donors, could be reached. 63 a Electron-rich phosphines were also reported by Beller, Rivard and Ruiz when using N-heterocyclic olefins (NHOPs) 67 as substituents as well as by Dielmann and coworkers using imidazolidin-2-imino substituents (IAPs) 68 and by Sundermeyer and coworkers using phosphazenyl groups (PAPs). 69 The latter exhibited even higher donor strengths than the YPhos ligands.…”

Formation of C−C, C−N, and C−O Links between Isonitrile, Cyclopentadienyl, and Hydroxide Ligands Bound to Molybdenum(III): Syntheses and Crystal Structures of μ-Aminocarbyne and μ-Amino-oxycarbene Dimolybdenum Complexes

“…The formation of new C−X bonds, where X = C, N, O, etc., through the mediation of transition metals is an important route to novel organic compounds and ligands. , For example, coupling reactions involving isocyanides have led to the successful synthesis of a wide variety of new nitrogen-containing organic ligands and compounds during the past decade. , These reactions can proceed either through metal-mediated reductive coupling of the isocyanides 5 or by consecutive insertion of isocyanides into M−C bonds to give N-chelated cyclic compounds. The insertion reaction can be initiated in various ways: by oxidative addition of alkyl halides to [M(RNC) n ] complexes, by addition of an excess of isocyanide to metal complexes, 4b, or by thermolysis .…”