Metal 1,3-Benzobis(thiophosphinoyl)methanediide complexes and a base-stabilized 2-silaallene derivative

• Main Author: Yang, Yifan
• Other Authors: School of Physical and Mathematical Sciences
• Format: Theses and Dissertations
• Language: English
• Published: 2013
• Subjects: DRNTU::Science::Chemistry::Organic chemistry::Organometallic compounds
• Online Access: http://hdl.handle.net/10356/53520
• Institution: Nanyang Technological University

The syntheses of metal bis(thiophosphinoyl) and 1,3-benzobis(thiophosphinoyl)methanediide complexes are reported. The reaction of bis(thiophosphinoyl)methane [CH2(Ph2P=S)2] with 1 equivalent of KOtBu and 1.2 equivalent of nBuLi, followed by the hydrolysis to form the 1,3-benzobis(thiophosphinoyl)methane [1,3-C6H4(PhP=S)2CH2]. Metal 1,3-benzobis- (thiophosphinoyl)methanediide complexes [{μ-1,3-C6H4(PhP=S)2C}M]2 (M = Mg, AlMe, Sn, Pb), which have a 1,3-dimetallacyclobutane structure, were then synthesized by the reaction of [1,3-C6H4(PhP=S)2CH2] with Mg(nBu)2, AlMe3, Sn[N(SiMe3)2]2 or Pb[N(SiMe3)2]2, respectively. Moreover, the reactivity of the tin(II) 1,3-benzobis(thiophosphinoyl)methanediide complex [{μ-1,3-C6H4(PhP=S)2C}Sn]2 toward Lewis acids is reported. The results show that the Cmethanediide-Sn bonds in [{μ-1,3-C6H4(PhP=S)2C}Sn]2 are polar and the Cmethanediide atom is nucleophilic. Hence, the lone pair of electrons on the tin atom is less favorable for bond formation. Furthermore, the synthesis of a base-stabilized 2-silaallene derivative [(PPh2S)2CSiC(PPh2S)2] and its reactivity toward unsaturated substrates is also reported. The results show that [(PPh2S)2CSiC(PPh2S)2] has a C¯—Si2+—C¯ ylidic skeleton.