Metal Complexes of Mesitylphosphine: Synthesis, Structure, and Spectroscopy

A series of primary phosphine homoleptic complexes
[ML4]n+Xn
(1, M = Ni, n = 0; 2, M = Pd,
n = 2, X = BF4;
3, M = Cu, n = 1, X = PF6;
4, M = Ag, n = 1, X = BF4; L
= PH2Mes, Mes =
2,4,6-Me3C6H2] was
prepared
from mesitylphosphine and Ni(COD)2,
[Pd(NCMe)4][BF4]2,
[Cu(NCMe)4]PF6, and
AgBF4, respectively. Reactions
of 1−4 with
MeC(CH2PPh2)3 (triphos) or
[P(CH2CH2PPh2)3]
(tetraphos) afforded the derivatives
[M(L‘)L]n+Xn
(L‘ = triphos; 6, M = Ni, n = 0;
7, M = Cu, n = 1, X = PF6;
8, M = Ag, n = 1, X = BF4; L‘
= tetraphos; 9,
M = Pd, n = 2, X = BF4). Addition of
NOBF4 to 1 yielded the nitrosyl compound
[NiL3(NO)]BF4, 5.
The
solution structure and dynamics of 1−9 were
studied by 31P NMR spectroscopy (including the first
reported
analyses of a 12-spin system for 1−2).
Complexes 1, 3, 6, and
7·solvent were characterized
crystallographically.
The structural and spectroscopic studies suggest that the
coordination properties of L are dominated by its
relatively
small cone angle and that the basicity of L is comparable to that of
more commonly used tertiary phosphines.

本数据集涵盖一系列一级膦均配配合物[ML4]n+Xn，具体组成如下：1号配合物：M = Ni，n = 0；2号配合物：M = Pd，n = 2，X = BF4；3号配合物：M = Cu，n = 1，X = PF6；4号配合物：M = Ag，n = 1，X = BF4；配体L = PH2Mes，其中Mes = 2,4,6-Me3C6H2。上述配合物分别由均三甲苯基膦与二(1,5-环辛二烯)合镍(Ni(COD)2)、四(乙腈)合钯(II)四氟硼酸盐([Pd(NCMe)4][BF4]2)、四(乙腈)合铜(I)六氟磷酸盐([Cu(NCMe)4]PF6)以及四氟硼酸银(AgBF4)反应制备得到。
将配合物1−4与三(二苯基膦甲基)乙烷(triphos，即MeC(CH2PPh2)3)或四(二苯基膦乙基)膦(tetraphos，即[P(CH2CH2PPh2)3])进行反应，可得到衍生物配合物[M(L‘)L]n+Xn：当L‘为三(二苯基膦甲基)乙烷(triphos)时，6号配合物M = Ni，n = 0；7号配合物M = Cu，n = 1，X = PF6；8号配合物M = Ag，n = 1，X = BF4；当L‘为四(二苯基膦乙基)膦(tetraphos)时，9号配合物M = Pd，n = 2，X = BF4。
向配合物1中加入四氟硼酸亚硝酰(NOBF4)，得到亚硝酰配合物[NiL3(NO)]BF4（编号5）。
通过磷-31核磁共振(31P NMR)波谱法研究了配合物1−9的溶液结构与动态行为，其中包含首例针对配合物1和2的12自旋体系分析。
配合物1、3、6以及溶剂化配合物7·solvent经晶体学表征完成结构确证。
结构与波谱学研究表明，配体L的配位特性主要由其相对较小的锥角所决定，且该配体的碱性可与目前更常用的叔膦配体相媲美。