TY - JOUR
T1 - Silylated Ge 9 Clusters as New Ligands for Cyclic (Alkyl)amino and Mesoionic Carbene Copper Complexes
AU - Schiegerl, Lorenz J.
AU - Melaimi, Mohand
AU - Tolentino, Daniel R.
AU - Klein, Wilhelm
AU - Bertrand, Guy
AU - Fässler, Thomas F.
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/3/4
Y1 - 2019/3/4
N2 - The coordination of Ge 9 Zintl clusters at (carbene)Cu I moieties is explored, and the complexes [(CAAC)Cu] 2 [η 3 -Ge 9 {Si(TMS) 3 } 2 ] (1), (CAAC)Cu[η 3 -Ge 9 {Si(TMS) 3 } 3 ] (2), and (MIC)Cu[η 3 -Ge 9 {Si(TMS) 3 } 3 ] (3) are compared with their known N-heterocyclic carbene (NHC) derivatives (A and B), where CAAC = cyclic (alkyl)amino carbene, MIC = mesoionic carbene, and TMS = trimethylsilane. In analogy to the NHC derivatives, the synthesis of 1-3 proceeds by single-step reactions of (CAAC)CuCl or (MIC)CuCl with the [Ge 9 R 2 ] 2- and [Ge 9 R 3 ] - [R = Si(TMS) 3 ] cluster ligands, respectively, and yields complexes of (carbene)Cu I (carbene = CAAC, MIC) moieties exhibiting η 3 -coordination modes of the Ge 9 deltahedron to the Cu atom. In 1, [Ge 9 R 2 ] 2- acts as a η 3 -bridging unit for two (CAAC)Cu I moieties, and 2 and 3 feature single (carbene)Cu I (CAAC and MIC) fragments η 3 -connected to [Ge 9 R 3 ] - units. Analysis of the bond lengths in comparison with known examples shows a bond expansion within the coordinated Ge 3 triangular faces for all (carbene)Cu I Ge 9 complexes (carbene = NHC, MIC, CAAC). All compounds are characterized by single-crystal X-ray diffractometry, NMR spectroscopy [ 1 H, 13 C{ 1 H}, and 29 Si{ 1 H}], electrospray ionization mass spectometry, elemental analysis (C, H, and N), and for the first time also by IR and Raman investigations (for 2 and 3). The new complexes add to the known NHC derivatives and extend the exploration of Ge 9 clusters with carbene ligands at Cu I atoms.
AB - The coordination of Ge 9 Zintl clusters at (carbene)Cu I moieties is explored, and the complexes [(CAAC)Cu] 2 [η 3 -Ge 9 {Si(TMS) 3 } 2 ] (1), (CAAC)Cu[η 3 -Ge 9 {Si(TMS) 3 } 3 ] (2), and (MIC)Cu[η 3 -Ge 9 {Si(TMS) 3 } 3 ] (3) are compared with their known N-heterocyclic carbene (NHC) derivatives (A and B), where CAAC = cyclic (alkyl)amino carbene, MIC = mesoionic carbene, and TMS = trimethylsilane. In analogy to the NHC derivatives, the synthesis of 1-3 proceeds by single-step reactions of (CAAC)CuCl or (MIC)CuCl with the [Ge 9 R 2 ] 2- and [Ge 9 R 3 ] - [R = Si(TMS) 3 ] cluster ligands, respectively, and yields complexes of (carbene)Cu I (carbene = CAAC, MIC) moieties exhibiting η 3 -coordination modes of the Ge 9 deltahedron to the Cu atom. In 1, [Ge 9 R 2 ] 2- acts as a η 3 -bridging unit for two (CAAC)Cu I moieties, and 2 and 3 feature single (carbene)Cu I (CAAC and MIC) fragments η 3 -connected to [Ge 9 R 3 ] - units. Analysis of the bond lengths in comparison with known examples shows a bond expansion within the coordinated Ge 3 triangular faces for all (carbene)Cu I Ge 9 complexes (carbene = NHC, MIC, CAAC). All compounds are characterized by single-crystal X-ray diffractometry, NMR spectroscopy [ 1 H, 13 C{ 1 H}, and 29 Si{ 1 H}], electrospray ionization mass spectometry, elemental analysis (C, H, and N), and for the first time also by IR and Raman investigations (for 2 and 3). The new complexes add to the known NHC derivatives and extend the exploration of Ge 9 clusters with carbene ligands at Cu I atoms.
UR - http://www.scopus.com/inward/record.url?scp=85062107491&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.8b03338
DO - 10.1021/acs.inorgchem.8b03338
M3 - Article
C2 - 30741546
AN - SCOPUS:85062107491
SN - 0020-1669
VL - 58
SP - 3256
EP - 3264
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 5
ER -