Synthesis of Rh^I-σ-acetylide complexes in aqueous and non-aqueous solutions: molecular structures of [(PMe₃)₄Rh(CCPh)] and [(PMe₃)₃Rh(CCSiMe₃)]

Abstract

Attempted deprotonation of the cationic C ~S -[ R ~( P M ~, ) ~( H ) ( C ~C R ) ] C I salts with BunLi leads t o the formation of both [Rh(PMe3)4(C=_CR)] and [Rh(PMe3)4H] whereas the use of KOH/H20 yields exclusively the Rh' o-acetylides; the molecular structures of the trigonal-bipyramidal [Rh(PMe3)4(~CPh)] and square-planar [Rh(PMe3)3(CrCSiMe3)] complexes have been determined by X-ray diffraction.

The luminescent and scintillation properties of YAlO3 and YAlO3:Ce single crystalline films grown by liquid phase epitaxy from BaO‐based flux

“…A novel route to monomeric, oligomeric, and polymeric rhodium complexes was pioneered by Marder and co‐workers101, 102 through the direct oxidative addition of terminal alkynes to [L 4 RhMe] species, with loss of methane (in analogy to the synthesis of [Co(PMe) 4 (CCPh)] reported by Klein et al103 Terminal alkynes were found to react cleanly with [Rh(PMe) 4 ]Cl by oxidative addition to give cis ‐[Rh(PMe 3 ) 4 (CCR)(H)]Cl 104. The structure of this octahedral complex, as determined by X‐ray crystallography, exhibited bond lengths that indicated a lack of π back‐donation from the Rh d orbitals to alkynyl π* orbitals.…”

fac-Dichlorotris(trimethylphosphine)(trimethylphosphoniomethyl)rhodium(III) chloride/bromide dichloromethane benzene solvate

“…The fac-[RhCl 2 (CH 2 PMe 3 )(PMe 3 ) 3 ]Cl salt has been prepared by Marder, Fultz et al (1987) via a reaction of dichloromethane (DCM) with a 16-electron Rh I complex [RhCl(PMe 3 ) 3 ], and characterized by an X-ray crystal structure analysis of its DCM monosolvate, (Ia). We report here a solvated mixed-anion salt analogue of (Ia), obtained as a byproduct during our ongoing study of PMe 3 -containing rhodium-acetylide complexes (Zhu et al, 2006;Rourke et al, 2002;Rourke et al, 1995Rourke et al, , 2001Fyfe et al, 1991;Chow et al, 1989;Zargarian et al, 1989;Marder, Zargarian et al, 1987).…”

Metall‐Alkinyl‐σ‐Komplexe: Synthesen und Materialien

“…Eine neuartige Methode zur Synthese von Monomeren, Oligomeren und Polymeren, die die direkte oxidative Addition terminaler Alkine an L 4 RhMe unter Abspaltung von Methan umfasst, wurde von Marder et al [101,102] eingeführt (die Reaktion wird analog zu der von Klein et al [103] beschriebenen Synthese von [Co(PMe) 4 [106] Auf die Synthese anderer Übergangs-metalle wurde der Ansatz bislang nicht übertragen.…”