Solid-State 95Mo NMR Studies of Some Prototypal Molybdenum Compounds: Sodium Molybdate Dihydrate, Hexacarbonylmolybdenum, and Pentacarbonyl Phosphine Molybdenum(0) Complexes
Solid-State 95Mo NMR Studies of Some Prototypal Molybdenum Compounds: Sodium Molybdate Dihydrate, Hexacarbonylmolybdenum, and Pentacarbonyl Phosphine Molybdenum(0) Complexes
复制标题
一些原型钼化合物的固态 95Mo NMR 研究：二水合钼酸钠、六羰基钼和五羰基膦钼 (0) 配合物
DOI：
10.1021/jp9712415
复制
发表时间：
1997
影响因子：
2.9
通讯作者：
J. H. Nelson
中科院分区：
文献类型：
--
作者：
K. Eichele;R. Wasylishen;J. H. Nelson
从26 MHz(9.4T)的固体95Mo核磁共振测量获得了钼-95核四极偶合常数χ(95Mo)和四极不对称参数η。本文报道了首次从固体95Mo核磁共振谱直接测量1J(95Mo，13C)和1J(95Mo，31P)。首次报道了固体Mo(CO)6的13C/12C对95Mo屏蔽的影响： 1ΔMo(13/12C)=−0.316 ppm。涉及质子和钼的直接偶极自旋−自旋相互作用(即1H−95Mo)相对较弱，当用魔角自旋获得谱时，似乎对95Mo核磁共振线形没有显著贡献。六羰基钼被认为是固体95Mo核磁共振研究的一种有用的设置样品。对五羰基膦钼配合物的研究结果表明，固体95Mo核磁共振谱具有较高的稳定性。
Molybdenum-95 nuclear quadrupolar coupling constants, χ(95Mo), and quadrupolar asymmetry parameters, η, for sodium molybdate dihydrate, hexacarbonylmolybdenum(0), pentacarbonyl-5-methyldibenzophospholemolybdenum(0), and pentacarbonylbis(diphenylphosphino)methanemolybdenum(0) were obtained from solid-state 95Mo NMR measurements at 26 MHz (9.4 T). The first direct measurements of 1J(95Mo,13C) and 1J(95Mo,31P) from solid-state 95Mo NMR spectra are reported. Also, the first example of a 13C/12C isotope effect on 95Mo shielding is reported for solid Mo(CO)6: 1ΔMo(13/12C) = −0.316 ppm. Direct-dipolar spin−spin interactions involving protons and molybdenum (i.e., 1H−95Mo) are relatively weak and do not appear to make significant contributions to 95Mo NMR line shapes when spectra are acquired with magic-angle spinning. Hexacarbonylmolybdenum is proposed as a useful setup sample for solid-state 95Mo NMR studies. Our results for the pentacarbonyl phosphine molybdenum complexes indicate that solid-state 95Mo NMR st...