STUDIES OF [AG(PPH(3))(2)]NO3, [AG(P(CH2CH2CN)(3))(2)]NO3 AND [AG(P(C(6)H(4)ME-M)(3))(2)]NO3 BY X-RAY-DIFFRACTION AND SOLID-STATE NUCLEAR-MAGNETIC-RESONANCE

Solid-state magic angle spinning (MAS) P-31 NMR spectra of [Ag(PPh(3)) (2)]NO3 1, [Ag{P(CH2CH2-CN2)3}2]NO3 2 and [Ag{P(C(6)H(4)Me-m)(3)}(2)]N O3 3 have been obtained. In addition, the crystal structures for 2 and 3 have been determined. The results from the high-resolution NMR stud y are consistent with the known structure of 1 and the structures of 2 and 3. In each case the P-31 NMR spectra exhibit resolved splittings arising from Ag-107 and 109Ag with (1)J((AgP)-Ag-109-P-31) values of 5 24, 564 and 517 Hz for 1, 2 and 3, respectively. In 1 the two phosphor us nuclei are crystallographically non-equivalent, thus analysis of th e P-31 NMR spectrum indicates two chemically shifted phosphorus nuclei , delta(A) 9.50 and delta B 7.67, with (2)J((PAPB)-P-31-P-31) = 125 Hz . The two phosphorus nuclei of 2 are crystallographically and magnetic ally equivalent in the solid state as evident from the cross polarizat ion/MAS P-31 NMR spectrum, delta -9.56. Crystals of 2 are trigonal, sp ace group R(3) over barc$ a = 12.204(2), c = 26.418(5) Angstrom, Z = 6 . The Ag and P atoms are located on a three-fold rotation axis with Ag at the centre of inversion. The Ag-P bond distance is 2.383(1) Angstr om. The conformation of the cyanoethylphosphine ligands in 2 is analog ous to the ribs of an umbrella in which the silver atom is encapsulate d by the six cyano groups with an Ag...N separation of 3.439(2) Angstr om. The two phosphorus nuclei in 3 are crystallographically equivalent but magnetically non-equivalent since the molecule sits on a two-fold axis but lacks a centre of inversion. As a consequence of this symmet ry the two phosphorus nuclei have identical chemical shifts, delta 11. 2; however, (2)J((PP)-P-31-P-31) can be determined from slow MAS exper iments. For 3 the space group is orthorhombic Aba2, a = 15.142(1), b = 24.917(2), c = 10.2536(7) Angstrom, Z = 4. The two phosphorus atoms a re related by a crystallographically imposed two-fold axis. The nitrat e group is chelated symmetrically to the Ag atoms.