Pentacoordinated iridium( i )-cyclooctadiene complexes featuring a coumarin-functionalised imidazoline– or benzimidazoline–NHC ligand exhibit fluxional behavior as consequence of the hemilability pyrone ring in coumarin wingtip.

The chiral diphosphine ligand R,R-trans-1,2-C(6)H(10)(NHCOC(6)H(4)PPh(2))(2), 1, gives the fluxional trans-chelate complexes [M(1)]X, 2a-2c, M = Au or Ag. It is suggested that a similar trans-chelate conformation may be present in the catalytic intermediate [Pd(1)].

Optically active C 3-symmetric monoanionic ligands are uncommon in organometallic chemistry. Here we describe the synthesis of readily prepared tris(4 S-isopropyl-2-oxazolinyl)phenylborate [To (P)] and fluxional, zwitterionic four- and five-coordinate iridium(I) compounds [Ir(To (P))(eta (4)-C 8H 12)] ( 4) and [Ir(To (P))(CO) 2] ( 5). The highly fluxional nature of 4 and 5 makes structural assi...

A fluxional bis-monodentate ligand, based on the archetypal shape-shifting molecule bullvalene, self-assembles with M2+ (M=Pd2+ or Pt2+) to produce a highly complex ensemble of permanently coordination cages. Metal-mediated self-assembly selects for an M2L4 architecture while maintaining ligand complexity. second level simplification is achieved guest-exchange; binding halides within cage mixtu...

A new potentially hexadentate P(2)N(4) ligand has been prepared and its coordination chemistry to Pd(II) and Pt(II) investigated. The ligand bonds in a chelating fashion via the diphosphine backbone to PdCl(2) and PtCl(2) while the appended pyridyl groups remain non-bonding. Abstraction of the chloride ions from the platinum complex results in fluxional exchange of the pyridyl groups in solutio...

A series of [M (R2PC2H4PR:)(butadiene)] com plexes of Ni, Pd and Pt has been prepared and their structures investigated NMR-spectroscopically. The nickel and palladium com plexes, irre­ spective of the substituents at phosphorus, contain a fluxional ?/2-bonded butadiene m olecule. In the case of platinum the bonding mode is ligand dependent: an ^-arrangem ent is observed where R is tert-butyl o...

Thioether-phosphite ligands (SP’s) with axially chiral (S)-H0- or (S)-H8-binaphthyl moiety and their [Rh(COD)(SP)]BF4 complexes have been synthesized to study coordination chemistry catalytic features compare them those of the structurally analogous phosphine-phosphites (PP’s). NMR exchange studies on showed selective 1,5-cyclooctadiene dynamics. Firm evidence has found that this fluxional proc...

Highly unsaturated mono(N-heterocyclic carbene) Ir(iii) systems have been targeted via ligand abstraction protocols. Hydrogenation of Ir(IPr)(cod)Cl (1a) leads to the formation of the highly reactive (fluxional) trimer [Ir(IPr)(H)(2)Cl](3), while the related IMes system undergoes further C-H bond activation. Chloride abstraction from 1a prior to hydrogenation allows access to sources of the 12-...

The zinc complexes [(L1)(2)Zn(MeOH)(2)](OTf)(2), [(L1)ZnCl(2)], [(L2)ZnCl(2)], [(L2)Zn(OTf)(H(2)O)]OTf and [(Me-bispic)ZnCl(2)] of the ligands N-[(2-pyridyl)methyl]-2,2'-dipyridylamine (L1), N-[bis(2-pyridyl)methyl]-2-pyridylamine (L2) and N-methyl-[bis(2-pyridyl)methyl]amine (Me-bispic) were synthesised and characterised. The first copper(I) complexes of the ligands L1 and L2 were also synthes...