TY - JOUR
T1 - Utilising a Proton-Responsive 1,8-Naphthyridine Ligand for the Synthesis of Bimetallic Palladium and Platinum Complexes
AU - Multem, Arie J.H.
AU - Delaney, Andie R.
AU - Kroeger, Asja A.
AU - Coote, Michelle L.
AU - Colebatch, Annie L.
PY - 2024/2/1
Y1 - 2024/2/1
N2 - We present four proton-responsive palladium and platinum complexes, [MCl2(RPONNHO)] (M=Pd, Pt; R=iPr, tBu) synthesised by complexation of PdCl2 or PtCl2(COD) with the 1,8-naphthyridine ligand RPONNHO. Deprotonation of [MCl2(tBuPONNHO)] switches ligand coordination from mono- to dinucleating, offering a synthetic pathway to bimetallic PdII and PtII complexes [M2Cl2(tBuPONNO)2]. Two-electron reduction gives planar MI−MI complexes [M2(tBuPONNO)2] (M=Pd, Pt) containing a metal-metal bond. In contrast to the related nickel system that forms a metallophosphorane [Ni2(tBuPONNOPONNO)], an unusual phosphinite binding mode is observed in [M2(tBuPONNO)2] containing close phosphinite-naphthyridinone P⋅⋅⋅O interactions, which is investigated spectroscopically, crystallographically and computationally. The presented proton-responsive and structurally-responsive RPONNHO and bimetallic RPONNO complexes offer a novel platform for future explorations of metal-ligand and metal-metal cooperativity with palladium and platinum.
AB - We present four proton-responsive palladium and platinum complexes, [MCl2(RPONNHO)] (M=Pd, Pt; R=iPr, tBu) synthesised by complexation of PdCl2 or PtCl2(COD) with the 1,8-naphthyridine ligand RPONNHO. Deprotonation of [MCl2(tBuPONNHO)] switches ligand coordination from mono- to dinucleating, offering a synthetic pathway to bimetallic PdII and PtII complexes [M2Cl2(tBuPONNO)2]. Two-electron reduction gives planar MI−MI complexes [M2(tBuPONNO)2] (M=Pd, Pt) containing a metal-metal bond. In contrast to the related nickel system that forms a metallophosphorane [Ni2(tBuPONNOPONNO)], an unusual phosphinite binding mode is observed in [M2(tBuPONNO)2] containing close phosphinite-naphthyridinone P⋅⋅⋅O interactions, which is investigated spectroscopically, crystallographically and computationally. The presented proton-responsive and structurally-responsive RPONNHO and bimetallic RPONNO complexes offer a novel platform for future explorations of metal-ligand and metal-metal cooperativity with palladium and platinum.
KW - bimetallic
KW - palladium
KW - platinum
KW - proton-responsive ligand
KW - structurally-responsive
UR - http://www.scopus.com/inward/record.url?scp=85182418115&partnerID=8YFLogxK
UR - http://purl.org/au-research/grants/ARC/FL170100041
U2 - 10.1002/asia.202301071
DO - 10.1002/asia.202301071
M3 - Article
AN - SCOPUS:85182418115
SN - 1861-4728
VL - 19
JO - Chemistry - An Asian Journal
JF - Chemistry - An Asian Journal
IS - 3
M1 - e202301071
ER -