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Crystal structure of diiodo-bis[(4R,5R)-trans-4,5-bis[(diphenylphosphinomethyl)- 2,2-dimethyl-1,3-dioxalane]dicopper(I), Cu2I2(C31H32O2P2)2
Zeitschrift für Kristallographie - New Crystal Structures ( IF 0.3 ) Pub Date : 2006-04-01 , DOI: 10.1524/ncrs.2006.221.14.316 Y.-H. Deng , Y.-L. Yang , X.-J. Yang
Zeitschrift für Kristallographie - New Crystal Structures ( IF 0.3 ) Pub Date : 2006-04-01 , DOI: 10.1524/ncrs.2006.221.14.316 Y.-H. Deng , Y.-L. Yang , X.-J. Yang
C62H64C112I2O4P4, triclinic, PI (no. 1), a = 10.0989(2) A, b = 12.8084(1) A, c = 12.8423(2) A, a = 65.074(l)) β = 84.31°, γ = 87.854(1)°, V= 1499.0 A, Ζ = 1, R&(F) = 0.036, wRreffF) = 0.098, Τ = 293 Κ. Source of material The title compound was synthesized following a published procedure for the silver(I) analogs [1]. To a solution of optically pure DIOP (50.0 mg, 0.10 mmol; DIOP = (4fl,5A)-irans-4,5-bis[(diphenylphosphino)methyl]-2,2-dimethyl-l,3-dioxalane) in CH2CI2 (5 mL) was added an excess of Cul (40.0 mg, 0.21 mmol). After refluxing the mixture for 0.5 h, a precipitate was removed by filtration and the filtrate treated with dried diethyl ether (10 mL) to give a white powder (yield 76 %). Colorless crystals suitable for X-ray studies were obtained by slow evaporation of its solution in CH2Cl2/n-heptane (1:1). Elemental analysis found: C, 53.58 %; H, 4.82% (VarioEL); calc. for C62H64CU2I2O4P4: C, 54.04 %; H, 4.68%. Experimental details The absolute configuration of the chiral complex was confirmed by a value of the Flack parameter of 0.02(3) [2]. Discussion The chiral diphosphine DIOP is an important bidentate ligand for transition metal complexes that can be used for asymmetric catalytic reactions [3-5]. In the search for such complexes we have obtained a dimeric Cu(I) compound, [CuI(A,A-DIOP)]2, which features a novel Ο12 core quadruply bridged by all the four ligands. Each copper atom resides at a slightly distorted tetrahedral environment composed of two iodine atoms and two phosphorous atoms each from a DIOP ligand. The four bridging ligands and the two copper atoms form a rhombic four-membered G12I2 ring (I-Cu-1,109.11(6) and 110.42(6)°; Cu-I-Cu, 70.22(5)° and 70.24(5)°, respectively) and an outer 14-membered ring, CuDIOP-Cu-DIOP. Both of the Cul-Il-Cu2-I2 and Cul-Pl-P3Cu2-P4-P2 cores are coplanar (largest deviation 0.0069 A and 0.0317 A, respectively), intersecting at Cul—Cu2 with a dihedral angle of 97.4(6)°. The coordination parameters around the two Cu(I) centers are slightly different. The Cul—PI and Cul—P2 distances (2.252(4) A and 2.254(4) A) are shorter than the Cu2—P3 and Cu2—P4 distances (2.305(4) A and 2.320(4) A), while the Pl-Cul-P2 angle (122.5(2)°) is slightly wider than P3-Cu2-P4 (120.2(2)°). The bond angles about the two bridging iodine atoms are nearly identical (ZCu2-Il-Cul = 70.22(5)°; Z.Cu2-I2-Cul = 70.24(5)°). The Cu-Cu separation of 3.141 A indicates no significant interaction of the metals (the sum of the covalent radii is 2.76 A). Similar coordination mode has been reported for some Ag(I)-DIOP compounds [1] and ((4R,5R)-trans4,5-bis(((3-methylphenyl)phosphino)-methyl)-2,2-dimeth:yll,3-dioxalane)copper(I) chloride [5]. Table 1. Data collection and handling.
更新日期：2006-04-01
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