Reactivity of a Molecular Calcium Hydride Cation ([CaH]<sup>+</sup>) Supported by an NNNN Macrocycle
作者:Danny Schuhknecht、Thomas P. Spaniol、Yan Yang、Laurent Maron、Jun Okuda
DOI:10.1021/acs.inorgchem.0c01289
日期:2020.7.6
The hydride ligand in the cationic calcium hydride supported by a NNNN-type macrocycle, [(Me4TACD)2Ca2(μ-H)2(THF)][BAr4]2 (1; Me4TACD = 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane; THF = tetrahydrofuran; BAr4 = B(C6H3-3,5-Me2)4), shows, in addition to its Brönsted basicity toward weak acids, a pronounced nucleophilicity resulting in nucleophilic substitution or insertion (addition) at a silicon
NNNN型大环支撑的阳离子氢化钙中的氢化物配体[[Me 4 TACD)2 Ca 2(μ-H)2(THF)] [BAr 4 ] 2(1 ; Me 4 TACD = 1,4除了其对布朗斯台德的碱度外,还显示了,7,10-四甲基-1,4,7,10-四氮杂环十二烷; THF =四氢呋喃; BAr 4 = B(C 6 H 3 -3,5-Me 2)4)。弱酸,明显的亲核性导致在硅或sp 2碳中心发生亲核取代或插入(加成)。末端乙炔RC≡CH(R = SiMe 3环丙基)以及1,4-二苯基丁二烯被1脱质子化,得到双核络合物[(Me 4 TACD)2 Ca 2(μ-C≡CR)2 ] [BAr 4 ] 2(2a,R = SiMe 3 ;图2b,R =环丙基)和[(ME 4 TACD)2的Ca 2(μ 2 -η 4 -1,4--PH 2 c ^ 4 ħ 2)] [BAR 4 ] 2(3)用H 2演化。与BH的