The chemistry of heteroallyl derivatives of technetium. Reactivity of [TcNCl2(PPh3)2] and [Tc(CO)3Cl(PPh3)] with thiazetidine ligands, crystal structures of [Tc(CO)2(PPh3)2{PhNC(OEt)S}] and [TcN(Cl)(PPh3)-{PhNC(OEt)S}]
- 1 January 1990
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 2,p. 477-481
- https://doi.org/10.1039/dt9900000477
Abstract
The complex [Tc(CO)3Cl(PPh3)] reacts with the sodium salt of PhNC(OEt)SH to give the thiazetidine complex [Tc(CO)2(PPh3)2{PhNC(OEt)S}](1). The complex [TcNCl2(PPh3)2] reacts with an excess of the neutral ligand to give [TcN(Cl)(PPh3){PhNC(OEt)S}](2). When the reaction is carried out in presence of the ligand salt the disubstituted complex [TcN{PhNC(OEt)S}2](3) is obtained. The crystal structures of (1) and (2) were determined by X-ray crystallography and refined to conventional R factors of 0.0295 and 0.0649 respectively. Compound (1) is monoclinic, space group P21, with a= 12.825(5), b= 16.713(5), c= 9.480(5)Å, β= 94.29(3)°, and Z= 2. The technetium environment is distorted octahedral. Selected bond distances are: Tc–P(1) 2.423(1)Å, Tc–P(2) 2.456(1), Tc–S 2.529(1), Tc–N 2.228(5), and Tc–C 1.89(1)Å(mean). Compound (2) is triclinic, space group P, with a= 9.428(5), b= 10.237(5), c= 15.603(5)Å, α= 89.29(3), β= 102.74(3), γ= 115.61 (3)°, and Z= 2. The environment of Tc is distorted square pyramidal with the nidrido N atom as apex. Selected bond distances are: Tc–N (nitrido) 1.615(7), Tc–N (ligand) 2.135(7), Tc–S 2.375(3), Tc–Cl 2.366(2), and Tc–P 2.429(2)Å.Keywords
This publication has 26 references indexed in Scilit:
- The chemistry of heteroallene and heteroallyl derivatives of rhenium. Part 2. Reactivity of [ReO(OR)Cl2(PPh3)2](R = Me or Et) with RNCS (R = Ph or p-MeC6H4). Crystal structure of the thiazetidine rhenium(V) complex [ReOCl2(PPh3){p-MeC6H4NC(OEt)–S}]J. Chem. Soc., Dalton Trans., 1988
- The chemistry of heteroallene and heteroallyl derivatives of rhenium. Part 1. Reactivity of mixed carbonyl(formamido)(phosphine)rhenium(I) complexes with RNCS (R = Ph or p-MeC6H4) and PhNCO. Crystal structure of the thiazetidine rhenium(I) complex [Re(CO)2(PPh3)2{PhNC(OEt)–S}]J. Chem. Soc., Dalton Trans., 1988
- Preparation and characterization of mixed amido, carboxylato or thiazolato carbonyl(phosphine)technetium(I) complexesTransition Metal Chemistry, 1986
- Reaction of the technetium(I)carbonyl complexes [Tc(PMe2Ph)3(CO)2Cl] and [Tc(PPh3)2(CO)3Cl] toward pseudo-allyl ligands such as triazenido, formamidinato, and acetamidinato. Crystal structures of [Tc(PMe2Ph)2(CO)2(p-CH3C6H4N:N:NC6H4CH3-p)] and [Tc(PMe2Ph)2(CO)2(C6H5N:C(CH3):NC6H5)]Inorganic Chemistry, 1985
- Comparison of the chemical and biological properties of trans-[Tc(DMPE)2Cl2]+ and trans-[Re(DMPE)2Cl2]+, where DMPE = 1,2-bis(dimethylphosphino)ethane. Single-crystal structural analysis of trans-[Re(DMPE)2Cl2]PF6Inorganic Chemistry, 1985
- Synthesis and characterization of new formamido-complexes of rhenium(I). The crystal structure of [Re(CO)2(p-NO2C6H4NCHO) (PPh3)2]Inorganica Chimica Acta, 1983
- The crystal and molecular structure of trans-bis(triphenylphosphine)dicarbonyl(1,3-diphenylformamidino)rhenium(I)Inorganica Chimica Acta, 1982
- Synthesis and characterization of new formamidino and triazenidocomplexes of rhenium(I): [Re(CO)2(PPh3)2(ArNxxxXxxxNAr)] (X = CH,N)Inorganica Chimica Acta, 1981
- The crystal and molecular structure of trans-bis(triphenylphosphine)dicarbonyl(1,3-di-p-tolyltriazenido)rhenium(I)Inorganica Chimica Acta, 1981
- Transition-metal nitrosyl compounds. Part III. (NN-dialkyldithiocarbamato)nitrosyl compounds of molybdenum and tungstenJ. Chem. Soc. A, 1969