McCready Matthew S, Puddephatt Richard J
Department of Chemistry, University of Western Ontario, London N6A 5B7, Canada.
ACS Omega. 2018 Oct 19;3(10):13621-13629. doi: 10.1021/acsomega.8b01860. eCollection 2018 Oct 31.
The reaction of [PtMe(6-dppd)], , where 6-dppd is a 1,4-bis(2-pyridyl)pyridazine derivative, with bromoalkanes BrCHR, having a hydrogen-bond donor group R, gave the corresponding chiral products of trans oxidative addition [PtBrMe(CHR)(6-dppd)], , R = COH; , R = 4-CHCOH; , R = 4-CHCHCOH; , R = 2-CHCHOH; , R = 4-CHB(OH); , R = 3-CHB(OH); and , R = 2-CHB(OH). Complex was formed in equilibrium with two isomers formed by cis oxidative addition, while the reaction of with BrCHCHCOH gave mostly [PtBrMe(6-dppd)], . The supramolecular chemistry was studied by structure determination of six of the platinum(IV) complexes, with emphasis on the preference of the hydrogen bond acceptor (O, pyridyl N, or Br atom), formation of monomer, dimer, or polymer, and self-recognition or self-discrimination in self-assembly. Complex formed a monomer with the OH···N hydrogen bond, and complexes and formed racemic dimers by complementary hydrogen bonding with self-discrimination between COH or B(OH) groups, respectively. Complexes , , and formed polymers by intermolecular hydrogen bonding with self-recognition, with containing OH···N and and containing OH···Br hydrogen bonds. It is concluded that there is no clear preference for the hydrogen bond acceptor group, and that the observed product depends also on the orientation of the hydrogen bond donor group.
[PtMe(6 - dppd)]（其中6 - dppd是一种1,4 - 双(2 - 吡啶基)哒嗪衍生物）与具有氢键供体基团R的溴代烷烃BrCHR反应，生成了相应的反式氧化加成手性产物[PtBrMe(CHR)(6 - dppd)]，R = COH； ，R = 4 - CH₂COH； ，R = 4 - CH₂CH₂COH； ，R = 2 - CH₂CH₂OH； ，R = 4 - CH₂B(OH)₂； ，R = 3 - CH₂B(OH)₂；以及 ，R = 2 - CH₂B(OH)₂。配合物 与通过顺式氧化加成形成的两种异构体处于平衡状态，而 与BrCH₂CH₂COH反应主要生成[PtBrMe(6 - dppd)]。通过对六种铂(IV)配合物进行结构测定研究了超分子化学，重点关注氢键受体（O、吡啶基N或Br原子）的偏好、单体、二聚体或聚合物的形成以及自组装中的自我识别或自我区分。配合物 通过OH···N氢键形成单体，配合物 和 通过分别与COH或B(OH)₂基团之间的互补氢键形成外消旋二聚体。配合物 、 和 通过分子间氢键形成聚合物并具有自我识别能力， 含有OH···N氢键， 和 含有OH···Br氢键。得出的结论是，对于氢键受体基团没有明显的偏好，并且观察到的产物还取决于氢键供体基团的取向。
