1994
DOI: 10.1039/dt9940001453
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Synthesis and characterization of neutral technetium(III) complexes with mixed S,P-bidentate phosphine–thiolate ligands. Crystal structure of [Tc(SCH2CH2PPh2)2(SCH2CH2PPh2O)]

Abstract: Reduction-substitution reactions of [TcO,] -with an excess of the mixed bidentate thiol-phosphine ligands H L" [ L1 = 2-(dipheny1phosphino)ethanethiolate; L2 = 2-(dipheny1phosphino)propanethiolate and L3 = 2-(diphenylphosphino)thiophenolate] gave neutral five-co-ordinate technetium( tit) complexes of the type [TcL",(O=L")] (n = 1 1 or 2 2). However, the aromatic phosphinethiol ligand (n = 3) gave six-co-ordinated [TcL3,] 3. The five-co-ordinated complexes are diamagnetic and exhibit a trigonal-bipyramidal geom… Show more

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Cited by 25 publications
(12 citation statements)
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“…Other related mononuclear transition metal complexes with S,P chelating phosphanylalkanethiolato ligands which have been structurally characterized include [MoX( S , P ‐SCH 2 CH 2 PPh 2 ) 2 ] n + ( n = 0, X = O;18 n = 1, X = Cp36), [Re(SCH 2 Ph)( S , P ‐SCH 2 CH 2 PPh 2 ) 2 ],22 [Tc( S , P ‐SC 6 H 4 PPh 2 ) 3 ],14 [Tc( S , P ‐SCH 2 CH 2 PPh 2 ) 2 ( S ‐SCH 2 CH 2 POPh 2 )],15 [FeCl(CO)(PPh 3 )( S , P ‐SC{( t Bu)(SCOMe)}CH 2 PPh 2 )],21[Fe{η 2 ‐C(OMe)S}P(OMe) 3 ( S , P ‐SC( t Bu)=CHPPh 2 )],24 [Ir(H)( S , P ‐SCH 2 CH 2 PPh 2 )( S , P ‐HSCH 2 CH 2 PPh 2 )(CO)] + ,17 [Ni( S , P ‐SCH 2 CH 2 PR 2 ) 2 ] (R = Me,23 Ph25). Complexes with tri‐, tetra‐ or hexadentate phosphanylalkanethiolato ligands which also have been studied are [Mo{ S , P , S ‐(SCH 2 CH 2 ) 2 PPh} 2 ],6 [Ni{ S , S , P , P ‐SCH 2 CH 2 P(Ph)CH 2 CH 2 CH 2 P(Ph)CH 2 CH 2 S}],20 and [Os{ P , P , S , S , S , S ‐P(CH 2 CH 2 S)(CH 2 CH 2 SSCH 2 CH 2 ) 2 P(CH 2 CH 2 S)}] 9…”
Section: Resultsmentioning
confidence: 99%
“…Other related mononuclear transition metal complexes with S,P chelating phosphanylalkanethiolato ligands which have been structurally characterized include [MoX( S , P ‐SCH 2 CH 2 PPh 2 ) 2 ] n + ( n = 0, X = O;18 n = 1, X = Cp36), [Re(SCH 2 Ph)( S , P ‐SCH 2 CH 2 PPh 2 ) 2 ],22 [Tc( S , P ‐SC 6 H 4 PPh 2 ) 3 ],14 [Tc( S , P ‐SCH 2 CH 2 PPh 2 ) 2 ( S ‐SCH 2 CH 2 POPh 2 )],15 [FeCl(CO)(PPh 3 )( S , P ‐SC{( t Bu)(SCOMe)}CH 2 PPh 2 )],21[Fe{η 2 ‐C(OMe)S}P(OMe) 3 ( S , P ‐SC( t Bu)=CHPPh 2 )],24 [Ir(H)( S , P ‐SCH 2 CH 2 PPh 2 )( S , P ‐HSCH 2 CH 2 PPh 2 )(CO)] + ,17 [Ni( S , P ‐SCH 2 CH 2 PR 2 ) 2 ] (R = Me,23 Ph25). Complexes with tri‐, tetra‐ or hexadentate phosphanylalkanethiolato ligands which also have been studied are [Mo{ S , P , S ‐(SCH 2 CH 2 ) 2 PPh} 2 ],6 [Ni{ S , S , P , P ‐SCH 2 CH 2 P(Ph)CH 2 CH 2 CH 2 P(Ph)CH 2 CH 2 S}],20 and [Os{ P , P , S , S , S , S ‐P(CH 2 CH 2 S)(CH 2 CH 2 SSCH 2 CH 2 ) 2 P(CH 2 CH 2 S)}] 9…”
Section: Resultsmentioning
confidence: 99%
“…2-4 Monodentate or bidentate phosphines as well as bidentate or tetradentate functionalized phosphines, with PN, PO, and PS or PN 2 O, PN 2 S, and P 2 N 2 donor atom sets, have been the most studied towards the [M᎐ ᎐ O] 3ϩ (M = Re or Tc) core. [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] Recently, water-soluble phosphines revealed also a great potential for biomedical applications. [20][21][22] In our laboratory we have been synthesizing new heterofunctionalized phosphine ligands, potentially tridentate and dianionic, 23…”
Section: Introductionmentioning
confidence: 99%
“…The pink product was found to convert slowly into the fuchsia Tc(III) complex [ 99g Tc(L 1 ) 2 (S-L 1 O)] when it was dissolved in chloroform and the resulting solution was allowed to evaporate under air. The crystal structure of the complex [ 99g Tc(L 1 ) 2 (S-L 1 O)] has been reported previously. , It comprises two bidentate L 1 ligands and an oxidized form of L 1 (S-L 1 O) acting as a monodentate ligand through the deprotonated thiol sulfur atom, and carrying the oxo−phosphorus(V) group. On the basis of these findings, we speculated that the structure of the pink complex could be formulated as [ 99g Tc(L 1 ) 2 (S-L 1 )] where S-L 1 represents the ligand L 1 that is coordinated to the metal center only through the negative sulfur atom.…”
Section: Methodsmentioning
confidence: 99%
“…In spite of the well-developed technetium chemistry with thiolate and phosphine ligands, studies on the reactivity of mixed polydentate phosphine−thiol ligands toward technetium, and more generally toward other transition metals, have appeared in the literature only recently. Examples are represented by the five-coordinate and six-coordinate technetium(III) species of the type [ 99g Tc{P(C 6 H 4 S- o ) 3 }(CNPr i ) n ] ( n = 1 or 2), prepared by reduction−substitution reactions of the potentially tridentate ligand P(C 6 H 4 SH- o ) 3 onto [ 99g TcO 4 ] - in the presence of isonitriles.…”
Section: Introductionmentioning
confidence: 99%