SYNTHESIS AND STRUCTURE OF THE CATIONIC TERT-BUTOXIDE COMPLEXES Y3(OR)7CL(THF)3+, Y2(OR)4CL(THF)4+, AND Y(OR)CL(THF)5+ - REPRESENTATIVES OF A NEW CLASS OF YTTRIUM ALKOXIDES
SYNTHESIS AND STRUCTURE OF THE CATIONIC TERT-BUTOXIDE COMPLEXES Y3(OR)7CL(THF)3+, Y2(OR)4CL(THF)4+, AND Y(OR)CL(THF)5+ - REPRESENTATIVES OF A NEW CLASS OF YTTRIUM ALKOXIDES
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DOI：
10.1021/ja00162a035
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发表时间：
1990-03-14
影响因子：
15
通讯作者：
ZILLER, JW
中科院分区：
文献类型：
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作者：
EVANS, WJ;OLOFSON, JM;ZILLER, JW
(C{sub5}Me{sub5}){sub2}Sm(1)和(C{sub5}Me{sub5}){sub2}Sm(THF){sub2}(2)将顺式二苯乙烯异构化为反式二苯乙烯。1与二苯乙烯的化学计量反应形成((C{sub5}Me{sub5}){sub2}Sm){sub2}({u}-{eta}{sup 2}-{eta}{sup 4}-PhCHCHPh)(3)。1与苯乙烯反应生成((C{sub5}Me{sub5}){sub2}Sm){sub2}({u}-{eta}{sup 2}-{eta}{sup 4}-CH{sub2}CHPh)(4)。在3和4中，两个(C{sub5}Me{sub5}){sub2}Sm单元配位在烯键的相反侧，使得Sm-Sm矢量以直角平分键。在每个络合物中，苯基碳原子被定向为与其中一个钐中心相互作用。在4中，Sm-C(C{sub5}Me{sub5})距离从2.678(18)到2.847(18){angstrom}，Sm-C(烯烃)距离从2.537(15)到2.732(15){angstrom}，苯环上的两个碳原子与一个Sm原子相距2.772(17)和2.850(16){angstrom}。3由正己烷在P2{sub1}2{sub1}2空间群中结晶，晶胞参数为a=12.156(6){angstrom}，b=14.405(9){angstrom}，c=15.628(2){angstrom}，V=2737(2){angstrom}{sup3}，Z=2，D{subcalcd}=1.24g cm{sup{-3}}。4由正己烷在Pbca空间群中结晶，晶胞参数为a=21.169(4){angstrom}，b=17.663(3){angstrom}，c=23.713(5){angstrom}，V=8866(3){angstrom}{sup3}，Z=8，D{subcalcd}=1.417 g cm{sup{-}3}。对基于3134个观测反射的模型进行了最小二乘修正，最终收敛到R{subF}=6.2%。
(C{sub 5}Me{sub 5}){sub 2}Sm (1) and (C{sub 5}Me{sub 5}){sub 2}Sm(THF){sub 2} (2) isomerize cis-stilbene to trans-stilbene. The stoichiometric reaction of 1 with stilbene forms ((C{sub 5}Me{sub 5}){sub 2}Sm){sub 2}({mu}-{eta}{sup 2}-{eta}{sup 4}-PhCHCHPh) (3). 1 reacts with styrene to form ((C{sub 5}Me{sub 5}){sub 2}Sm){sub 2}({mu}-{eta}{sup 2}-{eta}{sup 4}-CH{sub 2}CHPh) (4). In both 3 and 4, the two (C{sub 5}Me{sub 5}){sub 2}Sm units coordinate on opposite sides of the alkene bond such that the Sm-Sm vector bisects the bond at right angles. In each complex, phenyl carbon atoms are oriented to interact with one of the samarium centers. In 4, the Sm-C(C{sub 5}Me{sub 5}) distances range from 2.678 (18) to 2.847 (18) {angstrom}, the Sm-C(alkene) distances range from 2.537 (15) to 2.732 (15) {angstrom}, and two carbon atoms of the phenyl ring are positioned 2.772 (17) and 2.850 (16) {angstrom} from one samarium atom. 3 crystallizes from hexane in space group P2{sub 1}2{sub 1}2 with a = 12.156 (6) {angstrom}, b = 14.405 (9) {angstrom}, c = 15.628 (2) {angstrom}, and V = 2737 (2) {angstrom}{sup 3} with Z = 2 for D{sub calcd} = 1.24 g cm{sup {minus}3}. 4 crystallizes from hexane in space group Pbca with a = 21.169 (4) {angstrom}, b = 17.663 (3) {angstrom}, c = 23.713 (5) {angstrom}, and V = 8866 (3) {angstrom}{sup 3} with Z = 8 for D{sub calcd} = 1.417 g cm{sup {minus}3}. Least-squares refinement of the model based on 3134 observed reflections converged to a final R{sub F} = 6.2%.