5,6-Membered palladium pincer complexes of 1-thiophosphoryloxy-3-thiophosphorylbenzenes. Synthesis, X-ray structure, and catalytic activity.
Novel unsymmetrical ligands, 1-thiophosphoryloxy-3-thiophosphorylbenzenes 3a-d, bearing phosphine sulfide and thiophosphoryloxy moieties as coordinating sites, were found to undergo cyclometalation at the C-2 position of the central benzene ring in a reaction with bis(benzonitrile)palladium dichloride affording rare examples of nonsymmetrical pincer complexes, namely [2-{(thiophosphoryl)oxy}-6-(diphenylthiophosphoryl)phenyl]palladium chlorides 4a-d, containing 5- and 6-membered fused metallacycles with kappa3-SCS'-coordination. Molecular structures of the complexes were characterized by X-ray diffraction. These complexes demonstrated high catalytic activity for the Suzuki cross-coupling reactions of aryl bromides with phenylboronic acid.
Kozlov
V A
VA
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova str., Moscow, 119991, Russia.
Aleksanyan
D V
DV
Nelyubina
Yu V
YV
Lyssenko
K A
KA
Gutsul
E I
EI
Vasil'ev
A A
AA
Petrovskii
P V
PV
Odinets
I L
IL
D001555:Benzene Derivatives / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D009943:Organophosphorus Compounds / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*
C545914:1-thiophosphoryloxy-3-thiophosphorylbenzene; D001555:Benzene Derivatives; D009942:Organometallic Compounds; D009943:Organophosphorus Compounds; D010165:Palladium