TY - JOUR
T1 - Bonding and Reactivity of a Pair of Neutral and Cationic Heterobimetallic RuZn2 Complexes
AU - Miloserdov, Fedor M.
AU - Pécharman, Anne-Frédérique
AU - Sotorríos, Lia
AU - Rajabi, Nasir Ahmad
AU - Lowe, John P.
AU - Macgregor, Stuart Alan
AU - Mahon, Mary F.
AU - Whittlesey, Michael K.
N1 - Funding Information:
This project has received funding from the European Union’s Horizon 2020 research and innovation programme under Marie Skłodowska-Curie Grant Agreement 792674 (F.M.M.) and EPSRC (Grant EP/T019743/1 for A.-F.P., Grant EP/T019876/1 for L.S., and Grant EP/R020752/1 for N.A.R.).
Publisher Copyright:
© 2021 American Chemical Society.
PY - 2021/11/1
Y1 - 2021/11/1
N2 - A combined experimental and computational study of the structure and reactivity of two [RuZn2Me2] complexes, neutral [Ru(PPh3)(Ph2PC6H4)2(ZnMe)2] (2) and cationic [Ru(PPh3)2(Ph2PC6H4)(ZnMe)2][BArF4] ([BArF4] = [B{3,5-(CF3)2C6H3}4]) (3), is presented. Structural and computational analyses indicate these complexes are best formulated as containing discrete ZnMe ligands in which direct Ru–Zn bonding is complemented by weaker Zn···Zn interactions. The latter are stronger in 2, and both complexes exhibit an additional Zn···Caryl interaction with a cyclometalated phosphine ligand, this being stronger in 3. Both 2 and 3 show diverse reactivity under thermolysis and with Lewis bases (PnBu3, PCy3, and IMes). With 3, all three Lewis bases result in the loss of [ZnMe]+. In contrast, 2 undergoes PPh3 substitution with PnBu3, but with IMes, loss of ZnMe2 occurs to form [Ru(PPh3)(C6H4PPh2)(C6H4PPhC6H4Zn(IMes))H] (7). The reaction of 3 with H2 affords the cationic trihydride complex [Ru(PPh3)2(ZnMe)2(H)3][BArF4] (12). Computational analyses indicate that both 12 and 7 feature bridging hydrides that are biased toward Ru over Zn.
AB - A combined experimental and computational study of the structure and reactivity of two [RuZn2Me2] complexes, neutral [Ru(PPh3)(Ph2PC6H4)2(ZnMe)2] (2) and cationic [Ru(PPh3)2(Ph2PC6H4)(ZnMe)2][BArF4] ([BArF4] = [B{3,5-(CF3)2C6H3}4]) (3), is presented. Structural and computational analyses indicate these complexes are best formulated as containing discrete ZnMe ligands in which direct Ru–Zn bonding is complemented by weaker Zn···Zn interactions. The latter are stronger in 2, and both complexes exhibit an additional Zn···Caryl interaction with a cyclometalated phosphine ligand, this being stronger in 3. Both 2 and 3 show diverse reactivity under thermolysis and with Lewis bases (PnBu3, PCy3, and IMes). With 3, all three Lewis bases result in the loss of [ZnMe]+. In contrast, 2 undergoes PPh3 substitution with PnBu3, but with IMes, loss of ZnMe2 occurs to form [Ru(PPh3)(C6H4PPh2)(C6H4PPhC6H4Zn(IMes))H] (7). The reaction of 3 with H2 affords the cationic trihydride complex [Ru(PPh3)2(ZnMe)2(H)3][BArF4] (12). Computational analyses indicate that both 12 and 7 feature bridging hydrides that are biased toward Ru over Zn.
UR - http://www.scopus.com/inward/record.url?scp=85118741913&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.1c02072
DO - 10.1021/acs.inorgchem.1c02072
M3 - Article
C2 - 34661399
SN - 0020-1669
VL - 60
SP - 16256
EP - 16265
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 21
ER -