Copper(I) Complexes derived from Mono- and Diphosphino-Boranes: Cu→B Interactions Supported by Arene Coordination

The monophosphino-boranes o-iPr2P(C6H4)BR2 (1: R = Ph and 3: R = Cy) and diphosphino-boranes [o-R2P(C6H4)]2BPh (5: R = Ph and 6: R = iPr) readily react with CuCl to afford the corresponding complexes {[o-iPr2P(C6H4)BPh2]Cu(μ-Cl)}2 2, {[o-iPr2P(C6H4)BCy2]Cu(μ-Cl)}2 4, {[o-Ph2P(C6H4)]2BPh}CuCl 7, and {[o-iPr2P(C6H4)]2BPh}CuCl 8. The presence of Cu→B interactions supported by arene coordination within complexes 2, 7, and 8 has been unambiguously evidenced by NMR spectroscopy and X-ray diffraction studies. The unique η2-BC coordination mode adopted by complexes 7 and 8 has been thoroughly analyzed by density-functional theory (DFT) calculations.

单膦硼烷类化合物o-iPr₂P(C₆H₄)BR₂（1：R=Ph，3：R=Cy）与双膦硼烷类化合物[o-R₂P(C₆H₄)]₂BPh（5：R=Ph，6：R=iPr）可与氯化亚铜（CuCl）顺利反应，分别得到对应配合物{[o-iPr₂P(C₆H₄)BPh₂]Cu(μ-Cl)}₂（2）、{[o-iPr₂P(C₆H₄)BCy₂]Cu(μ-Cl)}₂（4）、{[o-Ph₂P(C₆H₄)]₂BPh}CuCl（7）以及{[o-iPr₂P(C₆H₄)]₂BPh}CuCl（8）。配合物2、7与8中存在由芳烃配位支撑的Cu→B相互作用，该作用已通过核磁共振（NMR）波谱学与X射线衍射（X-ray diffraction）研究得到明确证实。配合物7和8所采用的独特η²-BC配位模式，已通过密度泛函理论（DFT）计算完成了全面深入的分析。