对叔丁基四硫杂杯[4]芳烃和对叔丁基四磺酰基杯[4]芳烃的单核和双核钼与钨配合物：镍对杯芳烃配体骨架的轻松裂解

Mononuclear and dinuclear molybdenum and tungsten complexes of p-tert-butyltetrathiacalix[4]arene and p-tert-butyltetrasulfonylcalix[4]arene: facile cleavage of the calixarene ligand framework by nickel.

作者信息

Buccella Daniela, Parkin Gerard

机构信息

Department of Chemistry, Columbia University, New York, New York 10027, USA.

出版信息

J Am Chem Soc. 2008 Jul 9;130(27):8617-9. doi: 10.1021/ja803215x. Epub 2008 Jun 17.

DOI:10.1021/ja803215x

PMID:18557612

Abstract

The reactivity of p-tert-butyltetrathiacalix[4]arene, [S4CalixBut(OH)4], and p-tert-butyltetrasulfonylcalix[4]arene, [(SO2)4CalixBut(OH)4], toward Mo(PMe3)5H2, Mo(PMe3)6, and W(PMe3)4(eta2-CH2PMe2)H has been used to synthesize a series of mononuclear molybdenum and tungsten calixarene compounds that feature both coordinatively saturated and unsaturated metal centers, such as [S4CalixBut(OH)2(O)2]M(PMe3)3H2 (M = Mo, W), [(SO2)4CalixBut(OH)2(O)2]M(PMe3)3H2, [S4CalixBut(OH)2(O)2]Mo(PMe3)3, [(SO2)4CalixBut(OH)2(O)2]Mo(PMe3)3, and [(SO2)4CalixBut(OH)(O)3]M(PMe3)3H. Comparison with the related {[CalixBut(OH)2(O)2]M} complexes indicates that the chemistry of the system is strongly influenced by the nature of the calixarene linker, that is, CH2, S, and SO2. For example, in contrast to the methylene-bridged calixarene system, the thiacalixarene and sulfonylcalixarene systems readily coordinate a second metal center to form homo- and heterodinuclear complexes, namely {[S4CalixBut(O)4]}[M(PMe3)3H2]2, {[(SO2)4CalixBut(O)4]}[Mo(PMe3)3H2]2 and {[S4CalixBut(O)4]}[Mo(PMe3)3H2][W(PMe3)3H2]. Of most interest, incorporation of nickel into [S4CalixBut(OH)2(O)2]M(PMe3)3H2 using Ni(PMe3)4 results in cleavage of a C- bond to give [(SArButOH)(SArButO)3][M(PMe3)3H2][Ni(PMe3)2], an observation that is of relevance to the role that nickel plays in hydrodesulfurization catalysis.

摘要

对叔丁基四硫杂杯[4]芳烃（[S4CalixBut(OH)4]）和对叔丁基四磺酰基杯[4]芳烃（[(SO2)4CalixBut(OH)4]）与Mo(PMe3)5H2、Mo(PMe3)6及W(PMe3)4(η2-CH2PMe2)H的反应活性已被用于合成一系列具有配位饱和及不饱和金属中心的单核钼和钨杯芳烃化合物，如[S4CalixBut(OH)2(O)2]M(PMe3)3H2（M = Mo、W）、[(SO2)4CalixBut(OH)2(O)2]M(PMe3)3H2、[S4CalixBut(OH)2(O)2]Mo(PMe3)3、[(SO2)4CalixBut(OH)2(O)2]Mo(PMe3)3及[(SO2)4CalixBut(OH)(O)3]M(PMe3)3H。与相关的{[CalixBut(OH)2(O)2]M}配合物比较表明，该体系的化学性质受杯芳烃连接基的性质强烈影响，即CH2、S和SO2。例如，与亚甲基桥连的杯芳烃体系不同，硫杂杯芳烃和磺酰基杯芳烃体系容易配位第二个金属中心以形成同核和异核双核配合物，即{[S4CalixBut(O)4]}[M(PMe3)3H2]2、{[(SO2)4CalixBut(O)4]}[Mo(PMe3)3H2]2及{[S4CalixBut(O)4]}[Mo(PMe3)3H2][W(PMe3)3H2]。最有趣的是，使用Ni(PMe3)4将镍引入[S4CalixBut(OH)2(O)2]M(PMe3)3H2会导致一个C键断裂，生成[(SArButOH)(SArButO)3][M(PMe3)3H2][Ni(PMe3)2]，这一观察结果与镍在加氢脱硫催化中所起的作用相关。