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

Abstract

, 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

Crystal structure of tetrakis(isopropyldiphenylphosphine)- di(μ-iodo)dicopper(I), Cu2l2(PC15H17)4

“…Within the 1:2 stoichiometry, CuI(P/f3)2 complexes have been shown to exhibit a monomelic, three coordinate structure [4], in addition to the dimeric four coordinate structure. The latter situation was reported for the ligands PH2PI1, PMePh 2 , PMe 3 and P(C2Ph) 3 [5][6][7][8].…”

“…The environment around each copper center is a distorted tetrahedron and the I-Cu-I and P-Cu-P bond an- [5,[7][8], A significant spread of the geometrical parameters is hence noticed in these iodide complexes which is consistent with a peculiar softness of the P2Cu(//-I>2CuP2 core. In addition to the steric and electronic effects of the ligands on the geometry, this system appears to be easily distorted by non-bonding interactions and the packing constraints within the solid.…”

Solid-State and Solution Structural Properties of Copper(I) Compounds with Bidentate Phosphane Ligands

“…The structural assignment given in Scheme 1 is based a 1:2 ratio yields [Cu(dppe) 2 ]BF 4 (1). [Cu(dppe) 2 ]I (2), on the reported structures of [Cu 2 (dppf) 2 I 2 ] [7] [dppf: 1,1Ј-[Cu 2 (dppe) 3 I 2 ] (3), and [Cu 2 (dppe) 2 I 2 ] (4) are prepared un-bis(diphenylphosphanylferrocene)] and [Cu 2 (PhPH 2 ) 4 I 2 ] [8] der similar conditions from CuI and dppe in CH 2 Cl 2 or (PhPH 2 : phenylphosphane). The signals in the CPMAS 31 PCHCl 3 (1:2, 2:3, and 1:1 Cu I -to-ligand ratios).…”

Cyclohexylbis(hydroxymethyl)phosphane: A Hydrophilic Phosphane Capable of Forming Novel Hydrogen‐Bonding Networks

“…There are other CuI-phosphane complexes known, having a fourmembered Cu 2 I 2 core and terminal coordinated monodentate phoshane ligands (e.g. [CuI(PPh 2 Me) 2 ] 2 ·SO 2 , [22] [CuI(PH 2 Ph) 2 ] 2 [23] and [CuI(PMe 3 ) 2 ] 2 [24] ). Complex 6 represents the first example of a Cu(+1) complex containing functionalized monodentate phosphane ligands coordinated to a CuI dimer.…”