TY - JOUR
T1 - Formation of Heterobimetallic Complexes by Addition of d10-Metal Ions to cis-[(dppe)M(κC-2-C6F4PPh2)2] (M = Ni, Pd, and Pt)
AU - Gericke, Robert
AU - Bennett, Martin A.
AU - Privér, Steven H.
AU - Bhargava, Suresh K.
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/9/11
Y1 - 2017/9/11
N2 - The reactivity of [(dppe)M(κC-2-C6F4PPh2)2] (M = Ni (1Ni), Pd (1Pd), and Pt (1Pt); dppe = 1,2-bis(diphenylphosphino)ethane)) toward monovalent coinage metal ions (M′ = Cu, Ag, and Au) has been investigated. Two main isomers [(dppe)M(κC-2-C6F4PPh2)(μ-2-C6F4PPh2)M′Cl] (2PdAg, 2PdAu, 2PtCu, 2PtAg, and 2PtAu) and [(dppe)M(μ-2-C6F4PPh2)2M′Cl] (3PdCu, 3PdAg, and 3PtCu) could be detected. Quantum chemical calculations underpin the enhanced thermodynamic stability of [(dppe)M(κC-2-C6F4PPh2)(μ-2-C6F4PPh2)M′Cl] for combinations of the heavier metals. NBO calculations reveal attractive Pt···Cu and Pt···Ag interactions in complexes 2PtCu and 2PtAg, respectively. From the reaction of [(dppe)M(κC-2-C6F4PPh2)2] with an excess of [AuCl(tht)], a series of trinuclear complexes [(dppe)M(μ-2-C6F4PPh2)2(AuCl)2] (4NiAu2, 4PdAu2, and 4PtAu2) was prepared. Reaction of [(dppe)M(κC-2-C6F4PPh2)(μ-2-C6F4PPh2)M′Cl] with TlPF6 leads to the formation of cationic derivatives [(dppe)M(μ-2-C6F4PPh2)2M′]PF6 with P-M′-P (6PtAu) or P-M′-C (7PdAu, 7PtAu) bonding situations around the coinage metal.
AB - The reactivity of [(dppe)M(κC-2-C6F4PPh2)2] (M = Ni (1Ni), Pd (1Pd), and Pt (1Pt); dppe = 1,2-bis(diphenylphosphino)ethane)) toward monovalent coinage metal ions (M′ = Cu, Ag, and Au) has been investigated. Two main isomers [(dppe)M(κC-2-C6F4PPh2)(μ-2-C6F4PPh2)M′Cl] (2PdAg, 2PdAu, 2PtCu, 2PtAg, and 2PtAu) and [(dppe)M(μ-2-C6F4PPh2)2M′Cl] (3PdCu, 3PdAg, and 3PtCu) could be detected. Quantum chemical calculations underpin the enhanced thermodynamic stability of [(dppe)M(κC-2-C6F4PPh2)(μ-2-C6F4PPh2)M′Cl] for combinations of the heavier metals. NBO calculations reveal attractive Pt···Cu and Pt···Ag interactions in complexes 2PtCu and 2PtAg, respectively. From the reaction of [(dppe)M(κC-2-C6F4PPh2)2] with an excess of [AuCl(tht)], a series of trinuclear complexes [(dppe)M(μ-2-C6F4PPh2)2(AuCl)2] (4NiAu2, 4PdAu2, and 4PtAu2) was prepared. Reaction of [(dppe)M(κC-2-C6F4PPh2)(μ-2-C6F4PPh2)M′Cl] with TlPF6 leads to the formation of cationic derivatives [(dppe)M(μ-2-C6F4PPh2)2M′]PF6 with P-M′-P (6PtAu) or P-M′-C (7PdAu, 7PtAu) bonding situations around the coinage metal.
UR - http://www.scopus.com/inward/record.url?scp=85029180142&partnerID=8YFLogxK
U2 - 10.1021/acs.organomet.7b00145
DO - 10.1021/acs.organomet.7b00145
M3 - Article
SN - 0276-7333
VL - 36
SP - 3178
EP - 3188
JO - Organometallics
JF - Organometallics
IS - 17
ER -