TY - JOUR
T1 - Homobimetallic bis-NHC(Ptdvtms)2 Complexes for the Hydrosilylation of Alkenes
AU - Sauer, Michael J.
AU - Offorjindu, Jeff
AU - Zámbó, Greta G.
AU - Reich, Robert M.
AU - Kühn, Fritz E.
N1 - Publisher Copyright:
© 2024 The Author(s)
PY - 2024/3/1
Y1 - 2024/3/1
N2 - A series of six bimetallic bis-NHC(Ptdvtms)2 complexes 1–6 (dvtms = 1,1,3,3-tetramethyl-1,3-divinyldisiloxane) has been designed by expansion of the monometallic Markó-type system in anticipation of synergistic bimetallic cooperation. The new compounds are easily accessible using Karstedt's catalyst [Pt2(dvtms)3] as platinum(0) precursor and the respective bis-(imidazolium) salts (L1–6), deprotonated by potassium tert‑butoxide. Characterization via NMR spectroscopy (1H, 13C, 29Si, 195Pt) and SC-XRD reveals a strong similarity of this new complex class to the parent monometallic complexes. The hydrosilylation reactions of oct-1-ene or 1,1,1,3,3-pentamethyl-3-vinyldisiloxane (MMVi) with 1,1,3,5,5-heptamethyltrisiloxane (MDHM), respectively, are efficiently and selectively catalyzed with turn-over frequencies (TOF) of up to 78,000 h–1 after a significantly shortened induction period compared to their monometallic relatives. Mercury poisoning experiments demonstrate the superiority of bimetallic compared to monometallic systems in terms of stability when exposed to silanes.
AB - A series of six bimetallic bis-NHC(Ptdvtms)2 complexes 1–6 (dvtms = 1,1,3,3-tetramethyl-1,3-divinyldisiloxane) has been designed by expansion of the monometallic Markó-type system in anticipation of synergistic bimetallic cooperation. The new compounds are easily accessible using Karstedt's catalyst [Pt2(dvtms)3] as platinum(0) precursor and the respective bis-(imidazolium) salts (L1–6), deprotonated by potassium tert‑butoxide. Characterization via NMR spectroscopy (1H, 13C, 29Si, 195Pt) and SC-XRD reveals a strong similarity of this new complex class to the parent monometallic complexes. The hydrosilylation reactions of oct-1-ene or 1,1,1,3,3-pentamethyl-3-vinyldisiloxane (MMVi) with 1,1,3,5,5-heptamethyltrisiloxane (MDHM), respectively, are efficiently and selectively catalyzed with turn-over frequencies (TOF) of up to 78,000 h–1 after a significantly shortened induction period compared to their monometallic relatives. Mercury poisoning experiments demonstrate the superiority of bimetallic compared to monometallic systems in terms of stability when exposed to silanes.
KW - Bimetallic
KW - Induction period
KW - Mercury poisoning
KW - N-heterocyclic carbenes
KW - Platinum
KW - Silanes
UR - http://www.scopus.com/inward/record.url?scp=85184021634&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2024.123030
DO - 10.1016/j.jorganchem.2024.123030
M3 - Article
AN - SCOPUS:85184021634
SN - 0022-328X
VL - 1007
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
M1 - 123030
ER -