共查询到20条相似文献,搜索用时 15 毫秒
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Ying Kai Loh Lu Ying M. ngelesFuentes Dinh Cao Huan Do Simon Aldridge 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(15):4901-4905
Introduced here is a new type of strongly donating N‐heterocyclic boryloxy (NHBO) ligand, [(HCDippN)2BO]? (Dipp=2,6‐diisopropylphenyl), which is isoelectronic with the well‐known N‐heterocyclic iminato (NHI) donor class. This 1,3,2‐diazaborole functionalized oxy ligand has been used to stabilize the first acyclic two‐coordinate dioxysilylene and its Ge, Sn, and Pb congeners, thereby presenting the first complete series of heavier group 14 dioxycarbene analogues. All four compounds have been characterized by X‐ray crystallography and density‐functional theory, enabling analysis of periodic trends: the potential for the [(HCDippN)2BO]? ligand to subtly vary its electronic‐donor capabilities is revealed by snapshots showing the gradual evolution of arene π coordination on going from Si to Pb. 相似文献
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Maotong Xu Andrew R. Jupp Douglas W. Stephan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(11):3586-3590
The analogy of the reactivity of group 1 phosphides to that of FLPs is further demonstrated by reactions with CO, affording a new synthetic route to acyl‐phosphide anions. The reaction of [K(18‐crown‐6)][PtBu2] ( 1 ) with CO affords [(18‐crown‐6)K?THF2][Z‐tBuP=C(tBu)O] ( 2?THF2 ) as the major product, and the minor product [K6(18‐crown‐6)][(tBu2PCO)2]3 ( 3 ). Species 2 reacts with either BPh3 or additional CO to give [K(18‐crown‐6)][(Ph3B)tBuPC(tBu)O] ( 4 ) and [K(18‐crown‐6)][(OCtBu)2P] ( 5 ), respectively. The acyl‐phosphide anion 2 is thought to be formed by a photochemically induced radical process involving a transient species with triplet carbene character, prompting 1,2‐tert‐butyl group migration. A similar process is proposed for the subsequent reaction of 2 with CO to give 5 . 相似文献
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Moumita Pait Gargi Kundu Srinu Tothadi Suvendu Karak Shailja Jain Kumar Vanka Sakya S. Sen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(9):2830-2834
The reaction of SIPr, [1,3‐bis(2,6‐diisopropylphenyl)‐imidazolin‐2‐ylidene] ( 1 ), with C6F6 led to the formation of an unprecedented mesoionic compound ( 2 ). The formation of 2 is made accessible by deprotonation of the SIPr backbone with simultaneous elimination of HF. The C?F bond para to the imidazolium ring in 2 is only of 1.258(4) Å, which is the one of the shortest structurally authenticated C?F bonds known to date. The liberation of HF during the reaction is unequivocally proved by the addition of one more equivalent of SIPr, which leads to the imidazolium salt with the HF2? anion. To functionalize 2 , the latter reacted with B(C6F5)3 to give an unusual donor–acceptor compound, where the fluoride atom from the C6F5 moiety coordinates to B(C6F5)3 and the carbanion moiety remains unaffected. Such coordination susceptibility of the fluoride atom of a nonmetallic system to a main‐group Lewis acid (Fnon‐metal→BR3) is quite unprecedented. 相似文献