Catalytic hydrophosphination of alkenes using a chiral, air-stable primary phosphine, (R)-[2'-methoxy(1,1'-binapthalen)-2-yl]phosphine, (R)-MeO-MOPH2, proceeds under mild conditions with a zirconium catalyst, [κ(5)-N,N,N,N,C-(Me3SiNCH2CH2)2NCH2CH2NSiMe2CH]Zr (1), to selectively furnish anti-Markovnikov, air-stable secondary phosphines or tertiary phosphines with slight modification of the proto...

Bisphosphines Ph(2)P(CH(2))(n)PPh(2) (n = 1, 2, 4, 6) may be easily monobenzylated to generate cationic phosphine/phosphonium ligands [Ph(2)P(CH(2))(n)PPh(2)CH(2)Ph](+). These ligands may be doped into a catalytic reaction involving neutral complexes with labile phosphine ligands, and replacement of a neutral phosphine with a charged analogue renders the resulting complex amenable to electrospr...

The asymmetric unit of the title triangulo-triruthenium compound, [Ru(3)(C(25)H(22)As(2))(C(18)H(14)BrP)(CO)(9)]·0.3CHCl(3), contains one mol-ecule of the triangulo-triruthenium complex and one partially occupied disordered chloro-form solvent mol-ecule. The bis-(diphenyl-arsino)methane ligand bridges an Ru-Ru bond and the monodentate phosphine ligand bonds to the third Ru atom. Both the arsine...

The chemoenzymatic synthesis of a Lewis basic phosphine-phosphine oxide organocatalyst from a cis-dihydrodiol metabolite of bromobenzene proceeds via a palladium-catalysed carbon-phosphorus bond coupling and a novel room temperature Arbuzov [2,3]-sigmatropic rearrangement of an allylic diphenylphosphinite. Allylation of aromatic aldehydes were catalysed by the Lewis basic organocatalyst giving ...

An enantioselective phosphine-catalyzed transformation has been developed for the synthesis of chiral cyclobutene triesters and fluorinated spirocyclic compounds. The strategy involved a P(III)/P(V) redox cycling process, via in situ reduction phosphine oxide with phenylsilane. This catalytic methodology enabled functionalized cyclobutenes (24 examples, up to 94% ee). On occasion extension this...

This article discusses the concept of N-heterocyclic carbenes (NHCs) equipped with more than one functional moiety, which allows using these NHCs for multiple purposes. A pioneering example for such NHCs is N-phosphine oxide-substituted imidazolylidenes (PoxIms), and their synthesis and strategic use are highlighted. The utility of PoxIms by far exceeds the conventional use as multidentate liga...

An overview is given of the chemistry of tris(azolyl)phosphines with focus on their preparation and application in coordinationand organometallic chemistry and catalysis. These systems share with the more abundant tris(pyrazolyl)borates and -methanes the ability to function as tridentate nitrogen ligands with hemilabile character, but the additional phosphine donor site grants them bifunctional...

An effective synthesis of the hitherto unknown 1-imidoalkylphosphonium salts has been developed in the reported study. The crucial step in the method included the decarboxylative α-methoxylation of N-phthaloyl- or N-succinylamino acids to the corresponding N-(1-methoxyalkyl)imides, followed by the displacement of the methoxy group by the triarylphosphonium group through melting of the imide der...

In the title compound, [Rh(C(13)H(16)NO)(C(18)H(15)P)(CO)]·0.5C(3)H(6)O, the Rh atom exhibits a square-planar coordination geometry, being coordinated by the N and O atoms of the bidentate β-diketonato ligand, a P atom from the triphenyl-phosphine unit and a C atom from the carbonyl group. The asymmetric unit also contains a disordered half-mol-ecule, lying about an inversion center, of the ace...

In the title triangulo-triruthenium compound, [Ru(3)(C(25)H(22)As(2))(C(21)H(21)P)(CO)(9)], the bis-(diphenyl-arsino)methane ligand bridges a Ru-Ru bond and the monodentate phosphine ligand bonds to the third Ru atom. Both the phosphine and arsine ligands are equatorial with respect to the Ru(3) triangle. Additionally, each Ru atom carries one equatorial and two axial terminal carbonyl ligands....