Triangular [Ag3]3+ Complexes Supported by Picolyl‐Substituted N‐Heterocyclic Carbene Ligands

A series or 12 picolyl-coritainig NHC liqarid precursors arid their Ag-1 salts are reported. The complexes [Ag-3((s)im(CH(2)pyCl)(2)}(3)]X-3 [2(PF6)(3)], [Ag-3((s)im(CH(2)pyBr)(2)}(3)]X-3 [3(PF6)(3)], [Ag-3{(s)im(CH(2)isoquin)(2)}|(3)]X-3 [4(PF6)(3)], [Ag-3{5,6-Cl-2-benzim(CH(2)pY)(2)}(3)]X-3 [6(BF4)(3)], [Ag-3{5,6-Me(2-)benzim(CH2-py)(2))(3))X-3 [7(PF6)(3)], [Ag-3(benzim{CH(2)py-3,4-(OMe)(2)}(2))(3)]-X-3 [8(PF6)], [Ag-3(benzim{CH(2)py-3,5-(OMe)(2)}(2))(3)]-X-3 [9(PF6)3] [Ag-3(5,6-Me-2-benzim)CH(2)py-3,4-(OMe)(2)}(2))(3)]X-3 [10(PF6)(3)], [Ag-3{5,6-Me-2-benzim(CH(2)py-3,5-Me-2-4-OMe}(2))(3)]-X-3 [11(PF6)(3)], and [Ag-3(5-OMe-benzim(CH(2)py)(2)}(3)]X-3 [12(PF6)(3)] (X = PF6(-) or BF4(-)) each contain a central [Ag-3](3+) core spanned by three NHC ligands. The optically pure [Ag-3{(R,R)-cyclohaxylim(CH(2)py)(2)](3)](PF6)(3) [(R,R)-5(PF6)(3)] adopts a different coordination mode. All complexes were characterized by NIvIR spectroscopy and HRMS. In addition, complexes 3(PF6), (R,R-5(PF6), 6(RF4), 7(PF6), and 8(PF6) were characterized by single-crystal X-ray diffraction and found to exhibit Ag Ag distances of approximately 2.7 angstrom.