? 3 -Coordination and Functionalization of the 2-Phosphaethynthiolate Anion at Lanthanum(III)**
? 3 -Coordination and Functionalization of the 2-Phosphaethynthiolate Anion at Lanthanum(III)**
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DOI：
10.1002/ange.202100559
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发表时间：
2021
影响因子：
--
通讯作者：
Watt F
中科院分区：
文献类型：
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作者：
Watt F
研究了配合物（PN）2La（SCP）（2）[PN=N-（2-（二异丙基膦基）-4-甲基苯基）-2，4，6-三甲基苯胺]中2-磷炔硫醇根阴离子的η3-配位.与双核硫氰酸根桥联（PN）2La（μ-1，3-SCN）2La（PN）2（3）和叠氮桥联（PN）2La（μ-1，3-N3）2La（PN）2（4）配合物的结构比较表明，[SCP]−配位模式主要受电子因素而不是空间因素控制。量子力学研究揭示了[SCP]−配体的反键π*-轨道对络合物2的LUMO的巨大贡献，使其成为[SCP]−阴离子第一次官能化的理想前体。因此，配合物2与CAAC反应，诱导[SCP]−配体的选择性重排，形成第一个CAAC稳定的第15族-第16族雷酸盐型配合物（PN）2La{SPC（RCAAC）}（5 a，B，R=Ad，Me）。 基于DFT计算提出了SCP-到-SPC异构化的详细反应机理。
We present the η3‐coordination of the 2‐phosphaethynthiolate anion in the complex (PN)2La(SCP) (2) [PN=N‐(2‐(diisopropylphosphanyl)‐4‐methylphenyl)‐2,4,6‐trimethylanilide)]. Structural comparison with dinuclear thiocyanate‐bridged (PN)2La(μ‐1,3‐SCN)2La(PN)2(3) and azide‐bridged (PN)2La(μ‐1,3‐N3)2La(PN)2(4) complexes indicates that the [SCP]−coordination mode is mainly governed by electronic, rather than steric factors. Quantum mechanical investigations reveal large contributions of the antibonding π*‐orbital of the [SCP]−ligand to the LUMO of complex2, rendering it the ideal precursor for the first functionalization of the [SCP]−anion. Complex2was therefore reacted with CAACs which induced a selective rearrangement of the [SCP]−ligand to form the first CAAC stabilized group 15–group 16 fulminate‐type complexes (PN)2La{SPC(RCAAC)} (5 a,b, R=Ad, Me). A detailed reaction mechanism for the SCP‐to‐SPC isomerization is proposed based on DFT calculations.