Structure of tetrafluoroboratotris(triphenylphosphine)copper(I). Cu(BF4)(P(C6H5)3)3. Example of a copper(I) complex containing a weakly coordinated tetrafluoroborate anion

Abstract

elusion is found in an examination of the geometry of the perchlorate group (Tables III and IV). The three Cl-0 distances not involving 0(2) are 1.383 (7), 1.392 (5), and 1.392 (5) A, with an average value of 1.389 (5) A; the Cl-0(2) distance of 1.434 (5) A is significantly longer than these three, as would be expected if 0(2) were involved in hydrogen bonding to the bridge. A view of the perchlorate anion and its probable interaction with the bridge is shown in Figure 2.The Cu-O-Cu bridging angle, , is 103.0 (2)°. The best unweighted least-squares line through the five available values of and 2/ for di-/r-hydroxo-copper(II) dimers has an intercept of 7730 cm'1 and a slope of -79.1 cm"1 deg"1. Using the published4 value for 2/of -410 cm"1, the predicted value of is 102.9 (1)°, which is in remarkable agreement with the observed angle. Evidently, therefore, the present structural data strongly support the hypothesis that, over the angular range 95°< < 105°, there is a linear relationship between and J. In the light of this observation, it should now be possible to predict J from or vice versa for this class of complexes.Registry No. [Cu(teen)0H]1(C104)1, 51259-55-3. Supplementary Material Available. A listing of structure factor amplitudes will appear following these pages in the microfilm edition of this volume of the journal. Photocopies of the supplementary material from this paper only or microfiche (105 X 148 mm, 24X reduction, negatives) containing all of the supplementary material for the papers in this issue may be obtained from the Journals

63Cu FT-NMR Studies of Tetrahedral Copper(I)-Phosphorus Complexes

“…All NMR samples were handled under strict exclusion of dioxygen using purified argon as the inert Cuprous complexes with the ligands mentioned above have been investigated in great detail, applying 31 P NMR [13], X-ray diffraction [14,15] conductivity measurements [16] or other techniques [17]. Although in many cases no crystal structure is available at present, tetrahedral or pseudotetrahedral geometry is assumed for CuL4X both in solution and in the crystalline state.…”

Structural and solid state 31P NMR studies of the four-coordinate copper(i) complexes [Cu(PPh3)3X] and [Cu(PPh3)3(CH3CN)]X

“…4(1)-109.77(9) • (average 102(4) • ). [7][8][9] Complexes with larger anions, such as PF 6 − and V(CO) 6 − , afford three-coordinate trigonal planar salts, [(PPh 3 ) 3 Cu]X with non-coordinated anion (Scheme 1(b)). 10, 11 Crystallization of the ClO 4 − , and PF 6 − complexes from acetonitrile solution does not result in solvated [(PPh 3 ) 3 CuX]•CH 3 CN complexes as observed for the halide complexes, but rather four-coordinate mixed ligand salts, [Cu(PPh 3 ) 3 (CH 3 CN)]X, in which the anion is displaced from the coordination sphere by acetonitrile (Scheme 1(c)).…”

Sulphur-ligand–metal complexes. Part 14. Bis[2-(3,3-dimethyl-2-thia-butyl)pyridine] complexes of copper(II) and related metal ions

“…This is confirmed by i.r. measurements of the anion absorptions (Table 2) as the splitting of the v3 band is about that expected for weak co-ordination of the anion to copper (11) .22930* 31 The nickel diaquo-complex is formulated as [NIL,-(H,O),][ClO,],, on the basis of the ionic nature of the v3(C104-) band, whereas the monoaqua-complexes clearly show features expected for co-ordinated c10,-,22932 and are therefore formulated as [ML,(H,O) (ClO,)]ClO, (M = Co or Ni).…”