The low temperature x-ray diffraction study of a trigonal planar, mixed olefin, complex of platinum (O) [Pt{P(C6H11)3} (C2H4)(C2F4)]

Howard, Judith A. K.; Mitrprachachon, P.; Roy, A.

doi:10.1016/s0022-328x(00)96091-1

Cited by 14 publications

(2 citation statements)

References 6 publications

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“…In [Rh(MCP) 2 (acac)], the only other MCP complex characterized by X-ray diffraction, the bond lengths were 1.405(19) and 1.440(19) Å, representing increases of 5.4% and 8.1%, respectively. The increase in MCP bond length upon coordination was much greater than the 1.5% increase in ethene CC bond length in the related complex [Pt(C 2 H 4 )(C 2 F 4 )(PCy 3 )]. , The C 2 F 4 bond increased by 10.0% upon coordination . The cyclopropyl rings in 7a were bent by 35.49° and 35.86° away from the plane of the double bond, a greater angle than those in the Rh complex (26.48° and 27.79°).…”

Section: Resultsmentioning

confidence: 85%

Mono- and Diphosphine Platinum(0) Complexes of Methylenecyclopropane, Bicyclopropylidene, and Allylidenecyclopropane

Hoyte

Spencer

2011

Organometallics

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Bicyclopropylidene (BCP) and methylenecyclopropane (MCP) belong to a class of alkenes that contain cyclopropyl rings with exocyclic double bonds. These alkenes have a rich chemistry and are active toward transition metal catalysts, particularly those of the group 10 metals. 1À4 However, the isolation of transition metal complexes containing these alkenes in η 2 -coordination has not received as much focus as their reactivity. Only a handful of η 2 -MCP complexes have been reported to date, 5À8 while there have been just two of η 2 -BCP, both of first-row transition metals. 7,8 A better understanding of the coordination chemistry of these interesting alkenes could provide valuable insight into their reactivity patterns. Despite the lack of isolated complexes, MCP and BCP are expected to be good ligands toward transition metals, with their high-lying HOMOs capable of effectively donating electron density into empty metal orbitals, 2,7 while alleviation of strain in the highly strained cyclopropyl rings upon coordination is a strong driving force for the formation of stable complexes. As platinum(0) is a strong π-donor, capable of effective back-donation, it is ideal for making the first late transition metal complexes of BCP. The successful synthesis of the Pt(0) complex [Pt(MCP)(PPh 3 ) 2 ] is a strong indication of the viability of such complexes. 5

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Section: Resultsmentioning

confidence: 85%

Mono- and Diphosphine Platinum(0) Complexes of Methylenecyclopropane, Bicyclopropylidene, and Allylidenecyclopropane

Hoyte

Spencer

2011

Organometallics

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“…Most of these complexes are distorted square planar (or trigonal planar) 16electron systems consisting of an olefin and two other ligands, with the chemical formula M(olefin)LL′ (M ) Pd, 8 Pt, 9,10 and Ni 11 ). Complexes of 16-electron systems with the formulas M(olefin) 2 L and M(olefin) 3 having a distorted pentagonal 12,13 and hexagonal geometry, 14,15 respectively, are much less common. To the best of our knowledge, there is still no pentagonal palladium(0) complex formulated as Pd(olefin) 2 L reported in literature.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of η²-Phosphonioalkene−Palladium(0) Complexes from Alkenylphosphonium Halides and Palladium(0) Species. Structure and Substitution Reactions of These Complexes

et al. 1997

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Treatment of Pd(dba)2 (dba = dibenzylideneacetone) with (trans-RCHCHPPh3)+Br- in dichloromethane afforded [Pd(trans-RCHCHPPh3)2Br]+ (R = CO2Et (4), CO2Me (5), Ph (6)). As shown by the results of the X-ray diffraction, 4 adopts a distorted pentagonal geometry with two EtO2CCHCH(PPh3)+ moieties and a bromide ligand. The C−C double bond in the EtO2CCHCH(PPh3)+ moieties are π-bonded to the palladium(0) center and are coplanar with the bromide ligand and the metal center. Both (EtO2CCHCHPPh3)+ moieties are oriented with the two PPh3 groups trans to each other and the olefin carbon that is attached to PPh3 occupying the coordination site neighboring to the bromide ligand. Treatment of trans-[R1CHCR2(PPh3)]+Br- with Pd(dba)2 in the presence of 1 equiv of PPh3 or P(OPh)3 gave the corresponding palladium complexes Pd[trans-R1CHCR2(PPh3)](L)Br (L = PPh3, R1 = Ph, R2 = H (3). L = PPh3, R1 = Me, R2 = H (7); R1 = CO2Et, R2 = H (8); R1 = CO2Me, R2 = H (9); R1 = H, R2 = Me (10). L = P(OPh)3, R1 = CO2Me, R2 = H (11)) in 54−92% yields. Substitution studies showed complexes 3 and 9 react with dppe (1,2-bis(diphenylphosphino)ethane) in dichloromethane to give [Pd(RCHCH(PPh3)(dppe)]+Br- (R = Ph (12); R = CO2Me (13)), but treatment of 9 and 11 with PPh3 and P(OPh)3, respectively, afforded only the original complexes on isolation.

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Structure of two stereoisomers of Pt(trans‐MeO₂CCHCHCO₂Me)₂[P(cyclohexyl)₃]: Complete assignment of the 11 non‐equivalent tricyclohexylphosphine protons using DQF‐COSY and ¹³C, ¹H two‐dimensional methods

Rüegger

1991

Magnetic Reson in Chemistry

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The 'H NMR spectrum of the Pt(0) complex Pt(trans-MeO,CCH=CHCO,Me), [ P(cyclohexyl), 1 was measured and the structures of the two isomeric forms, which differ with respect to olefin coordination, were assigned. The structural study made use of a complete analysis of the 11 nonequivalent protons of the P(cyclohexyl), in one isomer, and this was accomplished via DQF-COSY and "C,'H inverse heteronuclear correlation methods.

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The low temperature x-ray diffraction study of a trigonal planar, mixed olefin, complex of platinum (O) [Pt{P(C6H11)3} (C2H4)(C2F4)]

Cited by 14 publications

References 6 publications

Mono- and Diphosphine Platinum(0) Complexes of Methylenecyclopropane, Bicyclopropylidene, and Allylidenecyclopropane

Mono- and Diphosphine Platinum(0) Complexes of Methylenecyclopropane, Bicyclopropylidene, and Allylidenecyclopropane

Synthesis of η²-Phosphonioalkene−Palladium(0) Complexes from Alkenylphosphonium Halides and Palladium(0) Species. Structure and Substitution Reactions of These Complexes

Structure of two stereoisomers of Pt(trans‐MeO₂CCHCHCO₂Me)₂[P(cyclohexyl)₃]: Complete assignment of the 11 non‐equivalent tricyclohexylphosphine protons using DQF‐COSY and ¹³C, ¹H two‐dimensional methods

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The low temperature x-ray diffraction study of a trigonal planar, mixed olefin, complex of platinum (O) [Pt{P(C6H11)3} (C2H4)(C2F4)]

Cited by 14 publications

References 6 publications

Mono- and Diphosphine Platinum(0) Complexes of Methylenecyclopropane, Bicyclopropylidene, and Allylidenecyclopropane

Mono- and Diphosphine Platinum(0) Complexes of Methylenecyclopropane, Bicyclopropylidene, and Allylidenecyclopropane

Synthesis of η2-Phosphonioalkene−Palladium(0) Complexes from Alkenylphosphonium Halides and Palladium(0) Species. Structure and Substitution Reactions of These Complexes

Structure of two stereoisomers of Pt(trans‐MeO2CCHCHCO2Me)2[P(cyclohexyl)3]: Complete assignment of the 11 non‐equivalent tricyclohexylphosphine protons using DQF‐COSY and 13C, 1H two‐dimensional methods

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Synthesis of η²-Phosphonioalkene−Palladium(0) Complexes from Alkenylphosphonium Halides and Palladium(0) Species. Structure and Substitution Reactions of These Complexes

Structure of two stereoisomers of Pt(trans‐MeO₂CCHCHCO₂Me)₂[P(cyclohexyl)₃]: Complete assignment of the 11 non‐equivalent tricyclohexylphosphine protons using DQF‐COSY and ¹³C, ¹H two‐dimensional methods