Lewis Base Adducts of Group 11 Metal Compounds. part 24. Co-ordination of triphenylphosphine with silver nitrate. A solid-state cross-polarization magic angle spinning 31P nuclear magnetic resonance, crystal structure, and infrared spectroscopic study of

摘要

Solid-state cross-polarization magic angle spinning 31P n.m.r. spectroscopy, single-crystal X-ray structure determination, and i.r. spectroscopy have been used to investigate the properties of the adducts of triphenylphosphine with silver(1) nitrate: Ag( PPh,) NO,, (1); Ag( PPh,),NO,, (2); Ag( PPh,),NO,, (3); and Ag( PPh,),NO,, (4). The value of 'J(Ag-P) decreases with increasing co-ordination number: (1 ), 780; (2), 470; (3), 31 0; and (4), 190 Hz, paralleling solution results. Single-crystal X-ray structure determinations of compounds (2)-(4) have been performed: (2), triclinic, space group P i , a = 11.821 (3), b = 11.990(3), c = 13.660(3) A, u = 102.05(2), p = 11 2.80(2), and y = 105.30(2)", yielding R = 0.036 for 4 090 'observed' reflections; Ag-P 2.443(1) and 2.440(1) A, P-Ag-P 138.21 (5)"; (3), monoclinic, space group P2,/n, a = 18.984(5), b = 13.71 0(3), c = 17.900(4) A, and p = 94.94(2)", yielding R = 0.053 for 5 126 reflections; Ag-P 2.630(2), 2.525(1), and 2.545 2) A, P-Ag-P 11 8.37(5), 11 2.07(4), and 11 6.44(5)"; (4), trigonal, space group R3, a = 19.07(2) A , and u = 43.77(5)", yielding R = 0.060 for 1 903 observed reflections; Ag-P 2.643(3) and 2.671 (4) A, P-Ag-P 109.49(12) and 109.45(10)". Structures (2) and (3) [and (l)] are isomorphous with the analogous triphenylarsine compounds. In all cases the nitrate group is only weakly co-ordinated [and is ionic in (4) 3: Ag-0 2.464(4) and 2.649(4) in (2), 2.684(6) and 2.775(6) A in (3). These weak interactions are reflected in the small splitting observed for the asymmetric N-0 stretching vibrational mode compared to the analogous copper( I) compounds.