61586-84-3Relevant academic research and scientific papers
Exploring the coordination chemistry and reactivity of dialkylamino- and bis(dialkylamino)-phosphines in the coordination sphere of metals
Dyer, Philip W.,Fawcett, John,Hanton, Martin J.,Kemmitt, Raymond D.W.,Padda, Ranbir,Singh, Narendra
, p. 104 - 113 (2007/10/03)
The coordination chemistry of a range of dialkylamino- and bis(dialkylamino)-phosphines, RxP(NR′2) 3-x (x = 1 or 2; R = Cl, Me, Ph, C6F5; R′ = Et, Pri), 1-7, has been studied and the resulting Group 6 tetracarbonyl and platinum dichloride bis(phosphine) complexes fully characterised. Subsequently, the reactivity of the P-N bonds of the metal-bound phosphines was probed. Treatment of R″OH (R″ = Me, Et, allyl) solutions of the bis(dialkylaminodiphenylphosphine) complexes with anhydrous HCl gas led to substitution of NR′2 by OR″; the resulting P-alkoxy complexes were isolated in excellent yields. Acidification of ethylene glycol solutions of the aminophosphine complexes afforded the corresponding bis(chlorodiphenylphosphine) derivatives. Following reaction of trans-[W(CO)4(P{NEt2}Ph2)2] with either aqueous HCl or H2SO4, trans-[W(CO) 4(P{OH}Ph2)2] could be isolated as its dichloromethane solvate in excellent yield (81%). Reactions of the bis(bis{dialkylamino} phenylphosphine) complexes under identical conditions yielded a range of unidentified products. Reactions of ligands 1-7 with [{RhCl(CO)2}2] and elemental selenium have been undertaken and the products used to assess the phosphines' donor capabilities. Depending on the substituents at phosphorus, either trans-diphosphine or cis-dicarbonyl complexes result from reaction with [{RhCl(CO)2} 2]. The sterically demanding phosphine P(NPr2 i)2Ph (5) proved unreactive towards complexation with metals, although its selenide could be prepared and isolated. In order to probe the observed lack of oxidation or complexation the molecular structure P(NPr2i)2(C6F5) has been determined by X-ray crystallography. The Royal Society of Chemistry 2003.
ORGANOMETALLIC COMPLEXES WITH METAL-METAL BONDS XVI. SYNTHESIS OF NEW TRI- AND TETRAMETALLIC PLATINUM-MANGANESE COMPLEXES. CRYSTAL STRUCTURES OF
Braunstein, Pierre,Matt, Dominique,Bars, Odile,Louer, Michele,Grandjean, Daniel,et al.
, p. 79 - 108 (2007/10/02)
Reaction of cis-PtCl2(PPh2Cl)2 with NaMn(CO)5 in tetrahydrofuran yields new tri- and tetrametallic platinum-manganese complexes.The substitution of the Pt-Cl and P-Cl bonds is accompanied by a redox reaction, a labilization of the Pt-P bonds as exemplified by the isolation of complexes in which such bonds have been broken or created, and the rupture of one Mn-CO bond.The various complexes were separeted by column chromatography and the following tri- and tetrametallic complexes were characterized: Pt(CO)22, I, which is most likely to possess a linear Mn-Pt-Mn arrangement; , II, which was shown by X-ray diffraction to have a chiral PtMn2P2 framework with two Pt-Mn bonds (average 2.744(1) Angstroem forming an angle of 159.54(6) deg, and two PPh2 groups spanning these bonds; , III, which possesses one Pt-Mn bond (2.847(2) Angstroem) spanned by a PPh2 ligand, whereas the other Pt-Mn separation (3.618(2) Angstroem) does not correspond to a metal-metal bond, the metal being only connected by two PPh2 ligands; , IV, which is a centrosymmetric molecule characterized by the first planar heterotetrametallic chain (with Pt(1)Pt(1)'=2.669(1) Angstroem and Pt(1)Mn(1)=2.717(2) Angstroem and Mn(1)Pt(1)Pt(1)'=146.11(8) deg), and by one bridging PPh2 group on each Pt-Mn bond and two PPh2 bridges on the Pt-Pt bond.Almost planar pentacoordination is found for platinum in II and IV, and is most likely for III, but the hydrogen atom in the latter was not located by X-ray diffraction.The synthetic method used in this work appears promising for the preparation of novel heteropolymetallic complexes, although a detailed reaction mechanism cannot be proposed.
