Stephen Morton

Reactions of coordinated ligands. XII: Single-stage template syntheses of tetradentate macrocyclic phosphine complexes

Preparation des complexes de Ni et Pd. Structure cristalline et moleculaire de dichloro (tetrahydroxy octa methyl-tetraphosphacyclotetradecane)-Pd(II)

Reaktionen koordinierter liganden : X. Reaktivität zweikerniger eisencarbonylkomplexe mit sekundären phosphidobrüken μ-rph

Abstract The reaction between pentacarbonyliron(0) and phenylphosphane affords, depending on the conditions applied, the complexes (CO) 4 FePhPh 2 (I), (CO) 6 − Fe 2 (PhPH)2 (II) or [(CO) 3 Fe] 3 (PhP) 2 (III) in high yields and purity. Compound I reacts with (η-C 5 H 5 )Fe(CO)2Br in the presence of NEt 2 H to give the phosphido complex (CO) 4 Feue5f8PhPHue5f8Fe(CO) 2 (η-C 5 H 5 ) (IV). Deprotonation of II with MeLi yields the lithio-phosphido complexes (CO) 6 Fe 2 (PhPH)(PhPLi) (IIb) or (CO) 6 Fe 2 (PhPLi) 2 (IIa). By reaction of the PhPH groups in II with halophosphanes PhPCl 2 , PhPIue5f8PPhI and Ph 2 PCl the novel phosphido complexes (CO) 6 Fe 2 (PhP) n ( n ue5fb 3, 4) (VII, VIII), (CO) 6 Fe 2 (PhPPPh 2 ) 2 (V), and [(CO) 6 Fe 2 (PhPH)(PhP)] 2 PPh (IX) are accessible. With formaldehyde, compound II yields the hydroxymethyl-substituted derivative (CO) 6 Fe 2 (PhPCH 2 OH) 2 (X). The stereochemistry of the complexes is discussed on the basis of their 31 P NMR spectra.

Phosphaalkynes as ligands in organometallic chemistry. Syntheses and 31p NMR spectra of platinum(II), palladium(II) and rhodium(I) complexes of dη5-cyclopentadienyltetracarbonyl-μ-(3,3-dimethyl-1-phosphabutyne)dimolybdenum, [Mo2(CO)4(η-c5H5)2tBuCP)]

Abstract Syntheses of the complexes trans -[PtCl 2 (PR 3 )Mo 2 (CO) 4 (η 5 -C 5 H 5 ) 2 ( t BuCP)], (PR 3 =PEt 3 , PPr 3 , PBu 3 , PPh 2 Me, PPhMe 2 ) trans -[PdCl 2 (PBu 3 )Mo 2 (CO) 4 (η 5 -C 5 H 5 ) 2 ( t BuCP)], and trans [RhCl{(PF 2 NMe) 2 CO}Mo 2 (CO) 4 (η 5 -C 5 H 5 ) 2 ( t BuCP)] are described and their 31 P NMR spectra presented and discussed.

Design of systems with extended metal—metal interactions. Syntheses of mono- and di-nuclear rhodium(I) and iridium(I) complexes containing dienes, carbon monoxide, bipyridyl and the urea derivative OC(NMePF2)2

Abstract The deep purple-red [RhCl(CO)(bipy)], black [IrCl(CO)(bipy)], and orange [Rh(bipy) 2 ][BF 4 ] complexes (bipy = bipyridyl) are reported, as is the unusual hydride [IrH(bipy) 2 ]CH 2 Cl 2 . The newly synthesised dinuclear yellow/orange oxalato bridged compounds [{Rh(C 6 H 10 )} 2 (C 2 O 4 )] and [{Ir(C 8 H 12 )} 2 (C 2 O 4 )]can be converted into the purple-red [{Rh(CO) 2 } 2 (C 2 O 4 )] and blue-black [{Ir(CO) 2 } 2 (C 2 O 4 )] complexes, respectively.

Fluorophosphine complexes of rhodium(I) and iridium(I): towards the design of systems with extended metal−metal interactions. The crystal structure of [{IrCl(PF3)2}2]

A single-crystal X-ray structure determination of [{IrCl(PF3)2}2](1)[monoclinic, P21/n, a= 10.526(1), b= 10.346(2), c= 13.150(1)A, β= 101.46(1)°, R= 0.0481] has confirmed the existence of dimeric molecules with short intra- and inter-molecular irdium–iridium contacts and infinite zigzag chains of iridium atoms. Detailed consideration of the structure allows conclusions to be drawn about the design of other fluorophosphineiridium(I) complexes with extended metal–metal interactions. These conclusions have been tested by syntheses of a variety of complexes of RhI and IrI containing the ligands PF2(NMe2), PF(O2C6H4), and OC(NMePF2)2. The complex [{IrCl[OC(NMePF2)2]}2] probably has a structure involving extended metal–metal interactions.

Extended metal–metal interactions in fluorophosphine complexes of iridium(I)

The Solid state structure of [IrCl(PF3)2]2 consists of infinite zig-zag chains of iridium atoms with short inter-and intra-molecular Ir ⋯ Ir contacts; by contrast related complexes containing PF2NMe2 do not appear to have extended metal–metal interactions.