Eg Hope

Intermediates and action effects in the activation of carbon-fluorine bonds by eta(5)-pentamethylcyclopentadienylrhodium halide complexes; crystal structure of [{eta(5)-C5Me3[CH2C6F4P(C6F5)CH2](2)-1,3}RhBr](+)center dot Br-

The reaction between [(η 5 -C 5 Me 5 )RhBr(μ-Br)] 2 and the diphosphine, (C 6 F 5 ) 2 PCH 2 CH 2 P(C 6 F 5 ) 2 (dfppe), in benzene proceeded via the intermediate cation [(η 5 -C 5 Me 5 )RhBr(dfppe)] + , which underwent CF and CH bond activation and CC bond formation to give sequentially [{η 5 -C 5 Me 4 CH 2 C 6 F 4 P(C 6 F 5 )CH 2 CH 2 P(C 6 F 5 ) 2 }RhBr] + and then [{η 5 -C 5 Me 3 [CH 2 C 6 F 4 P(C 6 F 5 )CH 2 ] 2 -1,3}RhBr] + , as evidenced by mass spectrometry and NMR spectroscopy. The bromide salt of the final product ( 4c ) has been structurally characterized by X-ray diffraction. Compound 4c crystallizes in the triclinic space group P with a =10.616(1), b =13.904(2), c =14.911(1) A, α =66.86(1), β =86.38(1), γ =84.72(1)° and Z =2. Refinement gave final R 1 and wR 2 [ I =2 σ ( I )] values of 0.0581 and 0.1641, respectively, for 6837 unique reflections. In contrast to the BF 4 − salt, the Cl − and BPh 4 − salts of cation [(η 5 -C 5 Me 5 )RhCl(dfppe)] + undergo reaction upon thermolysis in benzene to give the cation [{η 5 -C 5 Me 3 [CH 2 C 6 F 4 P(C 6 F 5 )CH 2 ] 2 -1,3}RhCl] + .

Metal k-edge exafs (extended x-ray absorption fine structure) studies of CrO2F2 and MnO3F at 1OK

Abstract I.R. spectroscopy shows that the title compounds are monomeric in the solid state. Metal K-Edge EXAFS data have been obtained from the solids at 10K, and refined to give d(Cr-O) = 1.55A, d(Cr-F) = 1.71A, d(Mn-O) = 1.59A, and d(Mn-F) = 1.72A.

Preparation of high-oxidation-state platinum group metal fluorides in flow systems. Synthesis of the metal hexafluorides, MF6 (M Ru, Rh, Os, Ir, Pt), ruthenium pentafluoride tetramer, (RuF5)4, and the novel trimer, (RuF5)3

Abstract The fluorination of platinum metals under anhydrous conditions in a flow system yields the volatile metal hexafluorides (M  Ru, Rh, Os, Ir, Pt) in high yield. The flow fluorination of ruthenium also affords green {RuF5}4 and bright red {RuF5}3. In the case of palladium, no volatile products were observed, the only product of the reaction being PdII[PdIVF6].

The transition-metal fluorides and oxide fluorides as selective fluorinating agents for hydrohalogenoalkanes

Abstract The reactions of the transition-metal fluorides, ReF 7 , ReF 6 , OsF 6 , IrF 6 , UF 6 , RuF 5 , VF 5 and CrF 5 , and the transition-metal oxide fluorides, VOF 3 , MoOF 4 , WOF 4 , ReOF 4 , ReOF 5 , OsO 3 F 2 , OsO 2 F 3 , OsOF 5 and OsOF 4 , with a variety of hydrohalogenoalkanes have been studied. Some of the transition-metal compounds exhibit remarkable specificity in their reactions. For example, in the reaction of CH 2 Cl 2 with ReF 6 , 85% of available fluorine is used to yield CH 2 ClF whereas, with UF 6 , all of the available fluorine is utilised to give CHCl 2 F; like ReF 6 , ReOF 4 produces efficient halogen exchange, some 98% of the available fluorine yielding CH 2 ClF. The selectivity and reactivity will be discussed in terms of the oxidation state and coordination geometry of the transition metal fluorinating agents.

trans-Carbonyl(pentafluorophenyl-C)bis[(pentafluorophenyl)diphenylphosphine-P]iridium(I)

In trans-[Ir(C6F5){P(C6F5)(C6H5)2}2(CO)], the Ir—P and Ir—C distances are comparable to those of the triphenylphosphine analogue. F⋯F interactions appear to dominate the configuration, resulting in virtually eclipsed C6F5(Ir) and C6F5(P) rings.

Synthesis of Novel Transition-Metal Carbonyl Fluorides

Abstract In the 1970s systematic investigation of the preparation of a number of transition-metal carbonyl fluorides led to the publication of a rationale which appeared to explain the structures of existing compounds and predict the likely configurations of species which had yet to be discovered [1]. Recent investigations on the reactions of xenon difluoride with transition metal carbonyls in anhydrous HF solution by 19F and 13C n.m.r. has provided further insights into the nature of this interesting class of compounds.

Cis-dichloro(triethylphosphine-P) [tris(2,6-difluorophenyl)phosphite-P]platinum(II)

In cis-[PtCl 2 (C 18 H 9 F 6 O 3 P)(C 6 H 15 P)], the Pt-P and Pt-Cl distances are comparable to those of the triphenylphosphite analogue, while the P-Pt-P angle is ca 5° larger.

SYNTHESIS AND CRYSTAL-STRUCTURE OF DIOXOBIS(MU-PENTAFLUOROPHENYLIMIDO)DI-(MU-METHYLCYCLOPENTADIENYL)DIMOLYBDENUM

Abstract The reaction between C 6 F 5 NO 2 and [(η-MeC 5 H 4 )Mo(CO) 3 ] 2 yields the dioxobisimido complex, [(η-MeC 5 H 4 )MoO (η-NC 6 F 5 )] 2 ( 1 ). The X-ray crystal structure of compound 1 shows a cis arrangement of the methylcyclopentadienyl ligands and a puckered metallacyclic core.

Preliminary communicationSynthesis and crystal structure of dioxobis(μ-pentafluorophenylimido)di-(η-methylcyclopentadienyl)dimolybdenum

Abstract The reaction between C 6 F 5 NO 2 and [(η-MeC 5 H 4 )Mo(CO) 3 ] 2 yields the dioxobisimido complex, [(η-MeC 5 H 4 )MoO (η-NC 6 F 5 )] 2 ( 1 ). The X-ray crystal structure of compound 1 shows a cis arrangement of the methylcyclopentadienyl ligands and a puckered metallacyclic core.

Synthesis and crystal structure of dioxobis(μ-pentafluorophenylimido)di-(η-methylcyclopentadienyl)dimolybdenum

Abstract The reaction between C 6 F 5 NO 2 and [(η-MeC 5 H 4 )Mo(CO) 3 ] 2 yields the dioxobisimido complex, [(η-MeC 5 H 4 )MoO (η-NC 6 F 5 )] 2 ( 1 ). The X-ray crystal structure of compound 1 shows a cis arrangement of the methylcyclopentadienyl ligands and a puckered metallacyclic core.