A nonacoordinated bridging selenide in a tricapped trigonal prismatic geometry identified in undecanuclear copper clusters: syntheses, structures, and DFT calculations

Inorganic Chemistry
C W LiuZhenyang Lin

Abstract

Undecanuclear copper clusters, [Cu(11)(micro(9)-Se)(micro(3)-Br)(3)[Se(2)P(OR)(2)](6)] (R = Et, Pr, (i)Pr) (1a-c), were isolated along with closed-shell ion-centered cubes, [Cu(8)(micro(8)-Br)[Se(2)P(OR)(2)](6)] (PF(6)) (2a-c) and [Cu(8)(micro(8)-Se)[Se(2)P(OR)(2)](6)] (3a-c), from the reaction of [Cu(CH(3)CN)(4)](PF(6)), NH(4)[Se(2)P(OR)(2)], and Bu(4)NBr in a molar ratio of 2:3:2 in CH(2)Br(2). The molecular formulations of these clusters were confirmed by elemental analysis, positive FAB mass spectrometry, and multinuclear NMR ((1)H, (31)P, and (77)Se). (77)Se NMR spectra of Cu(11) clusters (1a-c) are of special interest as two inequivalent selenium nuclei of the diselenophosphate (dsep) ligand exhibit different scalar coupling patterns with the adjacent phosphorus nuclei. X-ray analysis of 1c reveals a Cu(11)Se core stabilized by three bromide and six dsep ligands. The central core adopts the geometry of a 3,3,4,4,4-pentacapped trigonal prism with a selenium atom in the center. The coordination geometry for the nonacoordinate selenium atom is tricapped trigonal prismatic. The X-ray structure 2a or 2c consists of a cationic cluster in which eight copper ions are linked by six diselenophosphate ligands with a central micro(8)...Continue Reading

References

Jan 22, 2002·Inorganic Chemistry·Ruiyao WangRichard J Staples
Dec 24, 2002·Inorganic Chemistry·John P Fackler
Apr 3, 2003·Chemical Communications : Chem Comm·Simon J ColesGemma L Thomas
May 15, 2003·Chemical Communications : Chem Comm·C W LiuJu-Chun Wang
May 18, 1998·Angewandte Chemie·Ramón VilarDavid J Williams

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Citations

Jun 30, 2012·Inorganic Chemistry·Yi-Juan LiC W Liu
Feb 28, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Rajendra S DhayalC W Liu
Jan 13, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·C W LiuJu-Chun Wang
Sep 13, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Bing LiC W Liu
Nov 23, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Srinivas Katam, Prabusankar Ganesan
Jan 31, 2014·Inorganic Chemistry·Jian-Hong LiaoC W Liu
Jan 25, 2020·Inorganic Chemistry·Rhone P Brocha SilalahiC W Liu

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