Preparation of Heterobimetallic Ketimido-Actinide-Molybdenum Complexes

Abstract

During our attempts to prepare paddlewheel actinide-molybdenum complexes of the type [(X)An(MesNPR 2 ) 3 Mo(CO) 3 ] (Mes= 2,4,6-trimethylphenyl; X= Cl or I; An = U or Th; R = i Pr or Ph) we have found that under certain conditions acetonitrile insertion reactions occur to give the hetero-bimetallic bridging ketimido species [ClAn(µ-MesNP i Pr 2 ) 2 (µ-MesNP i Pr 2 {µ-NCMe})Mo(CO) 3 ] (An = U, 1; Th, 2), [ClAn(µ-MesNPPh 2 ) 2 (µ-MesNPPh 2 {µ-NCMe})Mo(CO) 3 ] (An = U, 3; An = Th, 4), and [IAn(η 2 -MesNP i Pr 2 )(µ-MesNP i Pr 2 ){µ-NC(Me)N(Mes)P i Pr 2 }Mo(CO) 3 ] (An = U, 5; Th, 6). Structural and spectroscopic data confirms the assignment of a ketimido ligand bridging An(IV) and Mo(0) centers. The isolation of 1-6 is in contrast to our previously reported preparations of [(X)An(MesNPPh 2 ) 3 Mo(CO) 3 ] (

Comparative Insertion Reactivity of CO, CO2, tBuCN, and tBuNC into Thorium– and Uranium–Phosphorus Bonds

“…However, this result is similar to the product of (C 5 Me 5 ) 2 ZrPMes with 2 equiv of CH 3 CN: namely, (C 5 Me 5 ) 2 Zr­(NCCH 3 ) 2 PMes . The U–N bond distances in 6 of 2.168(4) and 2.173(4) Å are similar to those of previously reported uranium-ketimido complexes: ,− for example, (C 5 Me 5 ) 2 U­(NCPh 2 ) 2 at 2.179(6) and 2.185(5) Å.…”

f-Element heavy pnictogen chemistry

“…In this section, seminal examples in actinide phosphorus chemistry are highlighted, noting that aer initial work on phosphine derivatives that remains contemporaneous, 70,71 binding phosphines to amides has supported metal-metal bonds. [72][73][74][75] Fig. 6 Rare earth metal polyphosphorus complexes 46-49.…”

Cyclometalated iridium complexes based on monodentate aminophosphanes

“…As far as aminophosphanes of general formula NHRPR 2 or NR 2 PR 2 are concerned, different coordination modes have been reported, so far (Scheme 1). As a matter of fact, in mononuclear complexes, the expected monodentate κ P coordination 2 has been observed along with the η 2 coordination, 3 whereas the 1κ N ,2κ P coordination 4 has been reported in dinuclear complexes (Scheme 1-top). Additionally, a very limited number of examples of κ 2 C , P cyclometalated aminophosphano ligands have been reported, when NR 2 is N -indolyl 5 a,b or N -carbazolyl, 5 b or in the case that a phenyl group 2 f ,5 c is attached to nitrogen (Scheme 1-bottom).…”