A series of mononuclear quasi-two-coordinate copper(I) complexes employing a sterically demanding thiolate ligand

Inorganic Chemistry
Stanislav Groysman, R H Holm

Abstract

A series of two-coordinate thiolate complexes [Cu(SAr*)L] was synthesized as possible reactants in forming analogues of the active site of Mo/Cu-containing carbon monoxide dehydrogenase. Complexes with L = PPh(3) (1), 2,6-lutidine (2), and the N-heterocyclic carbene Pr(i)(2)NHCMe(2) (3) have been prepared by the reaction of [CuCl(PPh(3))(3)] (1) or [CuBr(SMe(2))] (2, 3) with ligand L and the exceptionally sterically encumbered ligand Ar*S = 2,6-bis(2,4,6-triisopropylphenyl)benzenethiolate(1-). The reaction of [CuBr(SMe(2))] with the thiolate in the absence of added L afforded trinuclear [Cu(3)(SAr*)(2)Br] (7). The carbene complex (3) undergoes Cu-C bond insertion with sulfur to form the thiourea complex [Cu(SAr*)(Pr(i)(2)Me(2)ImS)] (4). The complexes [Cu(Ar*)L] with L = tetrahydrothiophene (5) and 2,6-lutidine (6) were obtained by reaction of Ar*Li(OEt(2)) with CuBr/L. These species did not undergo clean Cu-C bond insertion with sulfur transfer agents; the disulfide Ar*SSCH(2)Ph (9) was isolated from the reaction of 6 with (PhCH(2)S)(2)S. The structures of all complexes and 9 were determined. Whereas 5 and 6 are strictly two-coordinate with linear C-Cu-L angles, 1-4 are quasi-two-coordinate because of weak 3d-C(ppi) interaction...Continue Reading

References

Nov 7, 1996·Chemical Reviews·Russ Hille
Dec 12, 2002·Proceedings of the National Academy of Sciences of the United States of America·Holger DobbekOrtwin Meyer
Oct 24, 2006·Inorganic Chemistry·Iliana MedinaMark J Fink
May 29, 2007·Journal of the American Chemical Society·Jun-Jieh WangR H Holm

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Citations

May 5, 2011·Inorganic Chemistry·Ramachandran AzhakarDietmar Stalke
Apr 10, 2012·Inorganic Chemistry·Skylar J FerraraJames P Donahue
Sep 26, 2012·Inorganic Chemistry·Santosh K SahooBhisma K Patel
Feb 14, 2012·Proceedings of the National Academy of Sciences of the United States of America·Xufang DuanHanyi Zhuang
Aug 8, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Katam SrinivasGanesan Prabusankar
Aug 19, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Pokpong RungthanaphatsophonJustin R Walensky
Apr 18, 2015·Chemical Communications : Chem Comm·Mahmood Azizpoor FardJohn F Corrigan
Jun 28, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Thilini S HollingsworthStanislav Groysman
Apr 6, 2011·Chemistry : a European Journal·Hassanatu B MansaraySimon Aldridge
Apr 24, 2010·Chemistry : a European Journal·Antonio Ruiz-MartínezSantiago Alvarez
Jan 17, 2012·Chemistry, an Asian Journal·Ramachandran AzhakarDietmar Stalke
Feb 23, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Will J HumennyJohn F Corrigan
Feb 9, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Marcello GennariCarole Duboc
Nov 30, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Bahareh Khalili Najafabadi, John F Corrigan
May 6, 2020·Topics in Current Chemistry·Sina Matavos-AramyanMohammad Hossein Jazebizadeh
Mar 4, 2011·Chemistry : a European Journal·Jarl Ivar van der VlugtMartin Lutz
Jul 2, 2021·Inorganic Chemistry·Yu LiuDeborah L Kays
Mar 8, 2019·Chemical Reviews·Andreas A DanopoulosPierre Braunstein
Sep 15, 2021·Inorganic Chemistry·Umesh I Kaluarachchige DonStanislav Groysman

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