Reactions of bis-scandium bridged phosphinidene complex,[LSc(μ-PAr)]_(2)(L=MeC(NDIPP)CHC(Me)(NCH_(2)CH_(2)N(^(i)Pr)_(2)),DIPP=2,6-(^(i)Pr)_(2)C_(6)H_(3);Ar=2,6-Me_(2)C_(6)H_(3))(1),with pinacolborane,catecholborane,a...Reactions of bis-scandium bridged phosphinidene complex,[LSc(μ-PAr)]_(2)(L=MeC(NDIPP)CHC(Me)(NCH_(2)CH_(2)N(^(i)Pr)_(2)),DIPP=2,6-(^(i)Pr)_(2)C_(6)H_(3);Ar=2,6-Me_(2)C_(6)H_(3))(1),with pinacolborane,catecholborane,and 9-borabicyclo[3.3.1]nonane(9-BBN)are reported.Complex 1 reacts with pinacolborane and catecholborane to give scandium pinacolate(2)and catecholate(3),showing B-O bond cleavage.These two scandium complexes contain an unusual[P(Ar)B(H)P(Ar)]^(2−)dianion,which displays aμ-η^(2):η^(2) coordination model.On the other hand,reaction of complex 1 with 9-BBN affords the B-H bond cleavage product,1,3-diphospha-2,4-diboracyclobutane(4).展开更多
Rare-earth metal complexes have been used as catalysts for many types of reactions.However,the mechanistic studies showed that basically,these various reactions proceeded withσ-bond metathesis of RE–E bond(RE:rare-e...Rare-earth metal complexes have been used as catalysts for many types of reactions.However,the mechanistic studies showed that basically,these various reactions proceeded withσ-bond metathesis of RE–E bond(RE:rare-earth metals;E:main group elements)or RE ions acting as Lewis acid centers to activate the polar functional groups of the substrates.In this article,a lutetium phosphinophosphinidene complex,with Lu=P double-bond character,was synthesized and structurally characterized.展开更多
基金the National Natural Science Foundation of China(Nos.21325210,21132002 and 21121062)the State Key Basic Research&Development Program(No.2012CB821600).
文摘Reactions of bis-scandium bridged phosphinidene complex,[LSc(μ-PAr)]_(2)(L=MeC(NDIPP)CHC(Me)(NCH_(2)CH_(2)N(^(i)Pr)_(2)),DIPP=2,6-(^(i)Pr)_(2)C_(6)H_(3);Ar=2,6-Me_(2)C_(6)H_(3))(1),with pinacolborane,catecholborane,and 9-borabicyclo[3.3.1]nonane(9-BBN)are reported.Complex 1 reacts with pinacolborane and catecholborane to give scandium pinacolate(2)and catecholate(3),showing B-O bond cleavage.These two scandium complexes contain an unusual[P(Ar)B(H)P(Ar)]^(2−)dianion,which displays aμ-η^(2):η^(2) coordination model.On the other hand,reaction of complex 1 with 9-BBN affords the B-H bond cleavage product,1,3-diphospha-2,4-diboracyclobutane(4).
基金supported by the National Natural Science Foundation of China(nos.21732007,21890721,21821002,21890722,and 21950410519)the Natural Science Foundation of Tianjin Municipality(nos.19JCJQJC62300 and 18JCYBJC21400)+2 种基金the Tianjin Research Innovation Project for Postgraduate Students(no.2019YJSB081)the Frontiers Science Center for New Organic Matter[Nankai University(no.63181206)]the K.C.Wong Education Foundation,and the Shanghai Municipal Committee of Science and Technology.
文摘Rare-earth metal complexes have been used as catalysts for many types of reactions.However,the mechanistic studies showed that basically,these various reactions proceeded withσ-bond metathesis of RE–E bond(RE:rare-earth metals;E:main group elements)or RE ions acting as Lewis acid centers to activate the polar functional groups of the substrates.In this article,a lutetium phosphinophosphinidene complex,with Lu=P double-bond character,was synthesized and structurally characterized.
