Structural determinations of four mono- and binuclear tertiary phosphine and arsine complexes of copper(I) chloride

Gill, J. T.; Mayerle, J. J.; Welcker, Peter S.; Lewis, David F.; Ucko, David A.; Barton, Donna; STOWENS, D.; Lippard, Stephen J.

doi:10.1021/ic50159a035

Cited by 147 publications

(50 citation statements)

References 65 publications

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“…The steric effects are evident fromothe long Cu-P bond distances of 2.251(3) and (Tables 6 and 9). The Cu-P bond lengths are analogous to those observed in other tetrahedrally coordinated copper(1) compounds with twophosphine ligands (47). The M u -P bond angle, 141.3(1)", is close to that of the four-coordinate nitrate complex (NO,)Cu(PCy,),, 140(1)", but it is significantly larger than those typically reported for systems with the less bulky PPh, groups: 127(1)" in (tfac)Cu(PPh,), (25), 131.2(1)" in (NO,)Cu(PPh,), (22), and 123.26(6)" in (BH,)Cu(PPh,), (23).…”

Section: Solid State Structural Datasupporting

confidence: 70%

The chemistry of copper(I) β-diketonate compounds. Part V. Syntheses and characterization of (β-diketonate)CuL_n species where L = PBu₃, PPh₃, and PCy₃; n = 1 and 2; crystal and molecular structures of (acac)Cu(PCy₃), (tfac)Cu(PCy₃), (hfac)Cu(PCy₃), and (hfac)Cu(PCy₃)₂

Shin¹,

Hampden‐Smith²,

Duesler³

et al. 1992

Can. J. Chem.

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. Can. J. Chem. 70, 2954 (1992). The compounds (P-diketonate)Cu(PR3),,, where P-diketonate = 1.1,1,5.5,5-hexafluoroacetylacetonate, hfac; 1,1,1-trifluoroacetylacetonate, tfac; and acetylacetonate, acac; R = rz-butyl (12-Bu), phenyl (Ph), and cyclohexyl (Cy); n = 1 and 2, have been prepared. The monotriorganophosphine adducts were prepared in high yield by the reaction of the sodium salt of the corresponding P-diketonate with [ClCu(PR,)] with elimination of sodium chloride. The bis(triorganophosphine) adducts were prepared by the reaction of (P-diketonate)Cu(PR,) with one equivalent of triorganophosphine. These species were characterized by 'H, "c, and "P NMR spectroscopy, lTIR spectroscopy, mass spectroscopy, and by combustion elemental analysis. Four examples were structurally characterized-by single crystal X-ray The distortion is believed to be dueo to the large steric demands of the PCy, ligands that result in long Cu-P bond distances of02.251(3) and 2.277(3) A, a large P---Cu-P angle of 141.3(1)", long C u -0 distances of 2.213(5) and 2.251(5) A, and a small M u -0 angle of 80.8(2)" compared to the corresponding values for (hfac)Cu(PCy,). No trends in C u -0 bond distances between the compounds can be discerned, within the limits of error on the data, that would clearly enable a comparison of thermodynamic parameters such as bond length -bond strength relationships as a function of the P-diketonate substituents. However, the spectroscopic data revealed a number of trends as a function of the P-diketonate substituents, including an increase of v (C---O and v(CS) in the order acac < tfac < hfac, analogous to the increase in their Lewis acidity. An increase in shielding of the ,'P resonance of the triorganophosphine ligands was observed in the order hfac < tfac < acac, consistent with expected inductive effects based on the electronegativity of the P-diketonate substituents.H. -K. SHIN, M. J. HAMPDEN-SMITH, E. N. DUESLER et T . T. K o n~s .Can. J. Chem. 70, 2954 (1992). On a prepart les composes (P-dicCtonate)Cu(PR,),, dans lesquels P-dicetonate = 1,1,1,5,5,5-hexafluoroacCtylacCtonate (hfac), 1,1 , 1-trifluoroacetylacetonate (tfac) et acCtylacCtonate (acac); R = 11-butyle (n-Bu), phenyle (Ph) et cyclohexyle (Cy); n = 1 et 2. On a prepare les adduits monotriorganophosphines avec d'excellents rendements par la reaction du sel de sodium du P-dicetonate correspondant avec le [ClCu(PR,)], avec elimination de chlorure de sodium. On a prepare les adduits bis(triorganophosphine) par la reaction des (P-dicCtonate)Cu(PR,) avec un equivalent de triorganophosphine. On a caracterise ces especes par RMN du 'H, du I3c et du 3 1~, par spectroscopie infrarouge par transformee de Fourier, par spectroscopie de masse et par analyse Clkmentaire par combustion. On a caractenst5 les structures de quatre exemples par le biais de la diffracticn des rayons X par un cristal unique 2 1'Ctat solide. Les c~istaux du (acac)CuPCy, sont tricliniques, groupe d'espace P I , avec a = 13.502(6), b = 13,691 (6)

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Section: Solid State Structural Datasupporting

confidence: 70%

The chemistry of copper(I) β-diketonate compounds. Part V. Syntheses and characterization of (β-diketonate)CuL_n species where L = PBu₃, PPh₃, and PCy₃; n = 1 and 2; crystal and molecular structures of (acac)Cu(PCy₃), (tfac)Cu(PCy₃), (hfac)Cu(PCy₃), and (hfac)Cu(PCy₃)₂

Shin¹,

Hampden‐Smith²,

Duesler³

et al. 1992

Can. J. Chem.

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“…ligands and the halides have a tremendous influence on the degree of association and resulting structure of such complexes (9,10). Spectroscopic characterization of these complexes has proven-to be somewhat problematic, however, and as a consequence of this they have been largely studied by X-ray crystallography (3,10).…”

Section: Introductionmentioning

confidence: 99%

Complex formation between cuprous iodide and phenyl phosphine: a nuclear magnetic resonance and X-ray crystallographic study

Batchelor¹,

Birchall²,

Faggiani³

1985

Can. J. Chem.

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, 928 (1985). The X-ray crystal structure of di-p,-iodobis[bis(phenylphosphine)co~per(I)] has been determined: R, = 0.0460. The crystals were monoclinic, space group Cc, a = 10.625(2) A, b = 25.1 15(8) A, c = 1 1.361(2) A, P = 105.929(15)", fw = 821.28, and Z = 4. The molecular structure consists of two C U I ( C~H~P H~)~ units bridged via the iodines so that each copper achieves tetrahedral coordination. Nuclear magnetic resonance data provides evidence that the phenylphosphines remain coordinated in solution but undergo rapid exchange at room temperature. qui sont relites par les iodes d'une fa~on telle que chaque atome de cuivre atteint une coordination tCtraCdrique. Sur la base des donnCes de la rmn, on peut affirmer que, en solution, les phCnylphosphines restent coordinnkes mais qu'elles subissent un Cchange rapide a la temptrature ambiante.[Traduit par le journal] Introduction phine, arsine) appeared to be potentially useful for investigaAlthough basicity and donor ability are well known propertions concerning the relative importance of steric and electronic ties of trivalent compounds of the group 5 elements there has factors because a large number of X-ray crystallographic been relatively little investigation of the coordination chemistry studies have shown that the steric bulk of both the neutral of hydrides and organohydrides of these elements other than nitrogen. Presumably this is because the tertiary derivatives, especially the triphenyl compounds, are much easier to work with and much less susceptible to oxidation. While it is reasonable to expect that the coordination chemistry of primary and secondary phosphines will be very similar to that of tertiary derivatives potential differences do exist. For example, there is evidence for the dissociation of P-H bonds with resultant formation of phosphido complexes (1). Also it has been noted that the order of basicity for phosphines is

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“…The strain in the P--Cu--P angles shown in the crystal structure of Cu(p3)C1 in comparison with the monodentate complex (Gill, Mayerle, Welcker, Lewis, Ucko, Barton, Stowens & Lippard, 1976) may suggest a possible explanation.…”

mentioning

confidence: 97%

Structure of chloro[1,1,1-tris(diphenylphosphinomethyl)ethane]copper(I)

Fife¹,

Mueh²,

Campana³

1993

Acta Crystallogr C

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Structural determinations of four mono- and binuclear tertiary phosphine and arsine complexes of copper(I) chloride

Cited by 147 publications

References 65 publications

The chemistry of copper(I) β-diketonate compounds. Part V. Syntheses and characterization of (β-diketonate)CuL_n species where L = PBu₃, PPh₃, and PCy₃; n = 1 and 2; crystal and molecular structures of (acac)Cu(PCy₃), (tfac)Cu(PCy₃), (hfac)Cu(PCy₃), and (hfac)Cu(PCy₃)₂

The chemistry of copper(I) β-diketonate compounds. Part V. Syntheses and characterization of (β-diketonate)CuL_n species where L = PBu₃, PPh₃, and PCy₃; n = 1 and 2; crystal and molecular structures of (acac)Cu(PCy₃), (tfac)Cu(PCy₃), (hfac)Cu(PCy₃), and (hfac)Cu(PCy₃)₂

Complex formation between cuprous iodide and phenyl phosphine: a nuclear magnetic resonance and X-ray crystallographic study

Structure of chloro[1,1,1-tris(diphenylphosphinomethyl)ethane]copper(I)

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Structural determinations of four mono- and binuclear tertiary phosphine and arsine complexes of copper(I) chloride

Cited by 147 publications

References 65 publications

The chemistry of copper(I) β-diketonate compounds. Part V. Syntheses and characterization of (β-diketonate)CuLn species where L = PBu3, PPh3, and PCy3; n = 1 and 2; crystal and molecular structures of (acac)Cu(PCy3), (tfac)Cu(PCy3), (hfac)Cu(PCy3), and (hfac)Cu(PCy3)2

The chemistry of copper(I) β-diketonate compounds. Part V. Syntheses and characterization of (β-diketonate)CuLn species where L = PBu3, PPh3, and PCy3; n = 1 and 2; crystal and molecular structures of (acac)Cu(PCy3), (tfac)Cu(PCy3), (hfac)Cu(PCy3), and (hfac)Cu(PCy3)2

Complex formation between cuprous iodide and phenyl phosphine: a nuclear magnetic resonance and X-ray crystallographic study

Structure of chloro[1,1,1-tris(diphenylphosphinomethyl)ethane]copper(I)

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The chemistry of copper(I) β-diketonate compounds. Part V. Syntheses and characterization of (β-diketonate)CuL_n species where L = PBu₃, PPh₃, and PCy₃; n = 1 and 2; crystal and molecular structures of (acac)Cu(PCy₃), (tfac)Cu(PCy₃), (hfac)Cu(PCy₃), and (hfac)Cu(PCy₃)₂

The chemistry of copper(I) β-diketonate compounds. Part V. Syntheses and characterization of (β-diketonate)CuL_n species where L = PBu₃, PPh₃, and PCy₃; n = 1 and 2; crystal and molecular structures of (acac)Cu(PCy₃), (tfac)Cu(PCy₃), (hfac)Cu(PCy₃), and (hfac)Cu(PCy₃)₂