Open AccessBonding and Reactivity of a Pair of Neutral and Cationic Heterobimetallic RuZn2 Complexes
Author(s) -
Fedor M. Miloserdov,
AnneFrédérique Pécharman,
Lia Sotorríos,
Nasir A. Rajabi,
John P. Lowe,
Stuart A. Macgregor,
Mary F. Mahon,
Michael K. Whittlesey
Publication year - 2021
Publication title -
inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 233
eISSN - 1520-510X
pISSN - 0020-1669
DOI - 10.1021/acs.inorgchem.1c02072
Subject(s) - chemistry , imes , cationic polymerization , reactivity (psychology) , phosphine , lewis acids and bases , thermal decomposition , frustrated lewis pair , ligand (biochemistry) , stereochemistry , medicinal chemistry , crystallography , polymer chemistry , carbene , organic chemistry , catalysis , medicine , alternative medicine , pathology , biochemistry , receptor
A combined experimental and computational study of the structure and reactivity of two [RuZn 2 Me 2 ] complexes, neutral [Ru(PPh 3 )(Ph 2 PC 6 H 4 ) 2 (ZnMe) 2 ] ( 2 ) and cationic [Ru(PPh 3 ) 2 (Ph 2 PC 6 H 4 )(ZnMe) 2 ][BAr F 4 ] ([BAr F 4 ] = [B{3,5-(CF 3 ) 2 C 6 H 3 } 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···C aryl interaction with a cyclometalated phosphine ligand, this being stronger in 3 . Both 2 and 3 show diverse reactivity under thermolysis and with Lewis bases (P n Bu 3 , PCy 3 , and IMes). With 3 , all three Lewis bases result in the loss of [ZnMe] + . In contrast, 2 undergoes PPh 3 substitution with P n Bu 3 , but with IMes, loss of ZnMe 2 occurs to form [Ru(PPh 3 )(C 6 H 4 PPh 2 )(C 6 H 4 PPhC 6 H 4 Zn(IMes))H] ( 7 ). The reaction of 3 with H 2 affords the cationic trihydride complex [Ru(PPh 3 ) 2 (ZnMe) 2 (H) 3 ][BAr F 4 ] ( 12 ). Computational analyses indicate that both 12 and 7 feature bridging hydrides that are biased toward Ru over Zn.