Insertion of acetylenes in the PdPd bond of Pd2 (Ph2 PCH2 PPh2)2 Cl2

Balch, Alan L.; Lee, Chung-Li; Lindsay, Catherine H.; Olmstead, Marilyn M.

doi:10.1016/s0022-328x(00)94092-0

Cited by 39 publications

(4 citation statements)

References 10 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For example, the reaction pattern of alkynes with 4 and 5 [26b,28] turned out to be different from those with the known Pd(I)-Pd(I) complex Pd 2 Cl 2 (dppm) 2 (dppm = bis(diphenylphosphino)methane) [29]. In the latter reaction, only one equivalent of alkyne attacked the Pd-Pd bond to give a so-called…”

Section: Synthesis Of Pd(i)-pd(i) Complexes With Labile Ligandsmentioning

confidence: 99%

From mononuclear to multinuclear complexes of palladium containing unsaturated hydrocarbon ligands

Kurosawa

2004

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

Section: Synthesis Of Pd(i)-pd(i) Complexes With Labile Ligandsmentioning

confidence: 99%

From mononuclear to multinuclear complexes of palladium containing unsaturated hydrocarbon ligands

Kurosawa

2004

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

“…2 shows that one methyl group is tipped towards one metal whereas the second is aimed at the other; protonation at one metal would render these methyl groups inequivalent. Warming to ambient temperature results in the smooth transformation of 10 to [~r~( p , --q ' :~~-(Me02C)C=C(H)C02Me)(C0)2(dppm)2][BF4] (11) in which migration of the hydride to the alkyne group to give a bridging vinyl group has occurred. This transformation is accompanied by the disappearance of the hydride resonance of 10 and the appearance of the vinyl signal at 6 4.62 in the 'H NMR spectrum.…”

Section: [Ir2(co)(pme3)(p-co)(p-dmad)(dppm)] (6)mentioning

confidence: 99%

“…First 3 does not react with methyl triflate, presumably owing to the greater congestion at the metals when the alkyne is perpendicular. Although the smaller proton does find access to one of the metals, yielding, at low temperature, a product analogous to 8 except having a perpendicular alkyne and a cis-diphosphine arrangement (see Scheme I), warming to ambient temperature results in migratory insertion and formation of a vinyl-bridged product (11). The latter transformation is not surprising, but the failure of the isomeric 8 to undergo the analogous rearrangement is curious, particularly since a number of parallel alkyne-to-vinyl transformations have been reported (5 1).…”

Section: [Ir2(co)(pme3)(p-co)(p-dmad)(dppm)] (6)mentioning

confidence: 99%

Parallel vs. perpendicular alkyne coordination in binuclear complexes. The first examples of reactivity differences in isomers differing in their alkyne coordination modes

George¹,

McDonald²,

Cowie³

1996

Can. J. Chem.

View full text Add to dashboard Cite

Abstract:The reaction of [Ir,(CO),(dppm),] (dppm = Ph,PCH,PPh,) with dimethyl acetylenedicarboxylate (DMAD) first yields [ I~~( c o )~(~, -~' :~~-D M A D ) (~~~~)~](2) in which the alkyne is bound parallel to the metal-metal axis and the diphosphines are bound in a trans arrangement at both metals. This metastable isomer slowly rearranges to the stable form, [ I~~( C O ) , (~, -~~:~~-D M A D ) (~~~~)~](3), in which the alkyne is now bound perpendicular to the metals and the diphosphines are bent back in a cis arrangement at both metals. The analogous species can be prepared by substituting hexafluoro-2-butyne (HFB) for DMAD; however, for the HFB adduct the isomer having the parallel geometry is seen only as a transient species; only Author to whom correspondence may be addressed. Telephone: (403) Can. J. Chem. Vol. 74, 1996 correspondant ainsi que des produits de dtcomposition. On a Ctabli la structure du composC 3 comme produit de solvatation double du chlorure de mtthylkne. Les donnCes cristallines sont les suivantes : 3.2CH,C12 : C6,H,4CI,06P41r2, monoclinique, groupe d'espace P2/c, a = 26,088(5) A, b = 9,896(4) A, c = 23,954(3) A, P = 109,27(1)", Z = 4, R(F) = 0,038, R,,(F~) = 0,0997 (tous les donnCes). [ I~~( C O )~(~, -~~:~~-H F B ) (~~~~)~]

show abstract

“…Addition of dimethyl acetylenedicarboxylate or hexafluoro-2-butyne to Rh 2 (dpm) 2 (y-C0)X 2 proceeds via reaction (14). (29) In the process the Rh-Rh separation increases by 0.60 Ä. of binuclear complexes.…”

Section: Rh-rh 2838(1) a (15) Of These Reactions Indicates The Presmentioning

confidence: 99%

Metal—Metal Bond Making and Breaking in Binuclear Complexes with Phosphine Bridging Ligands

Balch

1981

ACS Symposium Series

Self Cite

View full text Add to dashboard Cite

Polyfunctional phosphine ligands make useful bridging ligands for constructing binuclear metal complexes. This article is concerned with the use of two ligands -bis(diphenylphosphino)methane (dpm) and 2-diphenylphosphinopyridine (Ph 2 Ppy)-in promoting metal--metal bond forming and breaking reactions. Three specific topics will be covered. These are the ability of dpm to modify the stability of Rh-Rh bonds in interrelated compounds of Rh(I), Rh(II) and Rh(III), the utility of dpm bridging ligands in allowing novel metal-metal bond opening and closing in low valent rhodium and palladium complexes, and the usefulness of Ph 2 Ppy in the stepwise construction of binuclear complexes. Modification of Metal-Metal Bonding in RhodiumComplexes by a Bridging Diphosphine. The yellow, planar complexes, (RNC) 4 Rh + , undergo novel self-association reactions in concentrated solution to form the blue or violet dimers, (RNC) 8 Rh2 2+ , via reaction (1) (1,2). The equilibrium constants for this reaction are strongly L + (1) 2L-Rh-L L L = RNC influenced by solvent and by the size of the substituent on the isocyanide ligand. Not unexpectedly (t-BuNC) 4 Rh + with its bulky substituents is most reluctant to dimerize. Substitution of the bidentate dpm for half of the isocyanide ligands produces the blue, dimeric cation 1. (3) These dimers, which can be prepared with various isocyanide substituents including t-butyl, show no tendency to dissociate into monomers. Similar stabilization of the dimeric structure can be achieved by the use of bifunctional isocyanides like 1,3-diisocyanopropane. (4,5) These form qua-L L \ / Rh---/ \ / l _ 2 + 0097-6156/81/0155-0167$05.00/0

show abstract

Insertion of acetylenes in the PdPd bond of Pd2 (Ph2 PCH2 PPh2)2 Cl2

Cited by 39 publications

References 10 publications

From mononuclear to multinuclear complexes of palladium containing unsaturated hydrocarbon ligands

From mononuclear to multinuclear complexes of palladium containing unsaturated hydrocarbon ligands

Parallel vs. perpendicular alkyne coordination in binuclear complexes. The first examples of reactivity differences in isomers differing in their alkyne coordination modes

Metal—Metal Bond Making and Breaking in Binuclear Complexes with Phosphine Bridging Ligands

Contact Info

Product

Resources

About