Technetium(III) complexes with the tetradentate "umbrella" ligand tris(o-mercaptophenyl)phosphinate: x-ray structural characterization of Tc(P(o-C6H4S)3)(CNC3H7) and Tc(P(o-C6H4S)3)(CNC3H7)2

Vries, N. De; Cook, J.J.; Jones, Alun G.; Davison, Alan

doi:10.1021/ic00012a019

Cited by 43 publications

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“…While the latter Tc–P bond lengths are in the normal range for Tc–P single bonds, the Tc–P4 bond is among the shortest experimentally determined Tc–P distances . Only for the 16e – compound [Tc I (dppe) 2 Cl] and for a few Tc(III) complexes Tc–P bond lengths shorter than 2.3 Å have hitherto been reported. ,− The positions of the hydrido ligands have been determined from the final Fourier maps of the refinement of the crystal data and Tc–H bond lengths of 1.54(2), 1.55(4), and 1.64(5) Å have been derived. It is known that M–H bond lengths derived from X-ray diffraction experiments are commonly too short due to the elusive physical nature of the hydrido ligand electrons in such complexes, but no neutron diffraction data on technetium hydrido complexes have hitherto been reported.…”

Section: Resultsmentioning

confidence: 99%

Technetium Hydrides Revisited: Syntheses, Structures, and Reactions of [TcH₃(PPh₃)₄] and [TcH(CO)₃(PPh₃)₂]

2021

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Optimized synthetic approaches to [TcH 3 (PPh 3 ) 4 ] (1) and mer-trans-[TcH(CO) 3 (PPh 3 ) 2 ] (5) as key compounds of the technetium hydrido chemistry are reported. They give access to pure and stable samples of the complexes. The solid-state structures of the two title compounds have been determined. Reactions of [TcH 3 (PPh 3 ) 4 ] with monodentate basic phosphines such as PMe 2 Ph or PMe 3 lead to mixtures o f m i x e d -p h o s p h i n e c o m p l e x e s o f t h e c o m p o s i t i o n s [TcH 3 (PR 3 ) n (PPh 3 ) 4−n ] (n = 1−3), from which the mixed-phosphine trihydride complex [TcH 3 (PPh 3 ) 2 (PMe 3 ) 2 ] (2) could be isolated. Spectroscopic data and DFT calculations suggest a fluxional structure between a capped trigonal prism and a pentagonal bipyramid. Reactions of the monohydride mer-trans-[TcH(CO) 3 (PPh 3 ) 2 ] (5) with HX (X = Cl, Br, I) give [TcX(CO) 3 (PPh 3 ) 2 ] (6) complexes in good yields, while mer-trans-[Tc{η 1 -O(CR)O}(CO) 3 (PPh 3 ) 2 ] (7) or cis−trans-[Tc{η 2 -OO(CR)}(CO) 2 (PPh 3 ) 2 ] (8) complexes are formed with carboxylic acids depending on the substituent R and the conditions applied. Chelate formation of the formato ligand can also be obtained by thermal decarbonylation of the isolated mertrans-[Tc(η 1 -O(CH)O)(CO) 3 (PPh 3 ) 2 ] (7a) complex. The latter reaction is reversible, and the tricarbonyl compound is reformed when [Tc{η 2 -OO(CH)}(CO) 2 (PPh 3 ) 2 ] (8a) is exposed to CO gas. Reactions of [TcH(CO) 3 (PPh 3 ) 2 ] (5) with phenyl seleninic acid (PhSeOOH) in methanol give the tetranuclear cluster [{Tc(CO) 3 } 3 (μ 3 -OH)(μ 2 -O(SePh)O) 3 {Tc(CO) 3 }] (10) and a small amount of the bridged dinuclear oxalato complex [Tc 2 (CO) 6 (ox)(OPPh 3 ) 2 ] (11). The latter compound is the result of a complex reaction, which involves a metal-induced oxidation of methanol to formate and a subsequent C−C coupling of two formato ligands. The plausibility of the proposed mechanism is supported by the fact that the dimeric oxalato complex is much more efficiently formed when the formato complex [Tc{η 1 -O(CH)O}(CO) 3 (PPh 3 ) 2 ] (7a) is directly reacted with PhSeOOH. Exclusively the monomeric oxalato complex [Tc(η 2 -oxH)(CO) 2 (PPh 3 ) 2 ] ( 12) is formed during a reaction of mer-trans-[TcH(CO) 3 (PPh 3 ) 2 ] (5) with oxalic acid. The remaining proton of the Hox − ligand of [Tc(η 2 -oxH)(CO) 2 (PPh 3 ) 2 ] (12) can be removed by NEt 3 , and the ion pair (HNEt 3 )[Tc(η 2 -ox)(CO) 2 (PPh 3 ) 2 ] (13) is formed.

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Section: Resultsmentioning

confidence: 99%

Technetium Hydrides Revisited: Syntheses, Structures, and Reactions of [TcH₃(PPh₃)₄] and [TcH(CO)₃(PPh₃)₂]

2021

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“…metals in their lower oxidation states and those on the right-hand side of the transition-metal block). Within the context of the present study we note recent applications of this particular ligand to the chemistry of rhenium in intermediate and high oxidation states , and the tetradentate “umbrella” chelation demonstrated by P{SH} 3 toward Tc(III) . Tris(ethylenethiol)amine, N{S} 3 , offers the reverse ligating combination with a hard principal donor atom and up to three additional soft ligating centers.…”

Section: Introductionmentioning

confidence: 95%

Complexes of Multifunctional Phosphorus Ligands. Rhenium(V) Complexes of the Multidentate Phenoxyphosphine Ligands Bis(o-trimethylsilyloxyphenyl)phenylphosphine and Tris(o-trimethylsilyloxyphenyl)phosphine. Stepwise Elimination of Me₃SiX (X = Cl, OEt) from the Metal−Ligand System

et al. 1999

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The silylated aryloxo ligands bis(o-silyloxyphenyl)phenylphosphine (abbreviated PhP{OT}(2)) and tris(o-trimethylsilyloxyphenyl)phosphine (abbreviated P{OT}(3), where T = Me(3)Si) were prepared. Complexation reactions with O=ReCl(2)(OEt)(PPh(3))(2) and O=ReCl(3)(PPh(3))(2) proceed by displacement of one PPh(3) and the subsequent stepwise replacement of the OEt and/or Cl substituents. The new complex Re(O)Cl(2)[kappa(2)-(P,O)-(PhP{O}{OT})](PPh(3)), formed by elimination of Me(3)SiOEt, exists in diastereomeric cis and trans forms. Elimination of a second equivalent of Me(3)SiCl gives Re(O)Cl[kappa(3)-(P,O,O)-(PhP{O}(2))](PPh(3)). Similarly P{OT}(3) converts Re(O)Cl(2)(OEt)(PPh(3))(2) to ReOCl(2)[kappa(2)-(P,O)-(P{O}{OT}(2))](PPh(3)) (5) (structurally characterized as 5.0.875CH(2)Cl(2)): crystal data; triclinic P&onemacr;, a = 14.302(4) Å, b = 18.734(2) Å, c = 17.639(4) Å, alpha = 80.950(12) degrees, beta = 80.12(2) degrees, gamma = 81.76(2) degrees, Z = 4. Final R(1) and wR(2) values are 0.0852 and 0.1525, respectively on F(o)(2) > 2sigma(F(o)(2)) data (or 0.1948 and 0.2019 on all data). The phenoxy phosphine ligand in 5 is bound via P and one O to Re. The P atoms are mutually cis to each other and to the terminal oxygen on Re. Two ortho-trimethylsiloxy substituted phenyl rings dangle from the coordinated phosphorus atom. Complex 5 can be converted to Re(O)Cl[kappa(3)-(P,O,O)-(P{O}(2){OT})](PPh(3)) (6) by treatment with PPN(+) Cl(-) and 6 was also obtained by direct reaction of Re(O)Cl(3)(PPh(3))(2) with P{OT}(3) at higher temperatures. The complex 6 has been structurally characterized: crystal data triclinic, P&onemacr;, a = 10.1509(6) Å, b = 12.1123(8) Å, c = 16.2142(14) Å, alpha = 97.851(7) degrees, beta = 94.852(7) degrees, gamma = 96.889(6) degrees, Z = 2. Final R(1) and wR(2) values were 0.0303 and 0.0721 on F(o)(2) > 2sigma(F(o)(2)) data (or 0.0348 and 0.0742 on all data). The phenoxyphosphine ligand in 6 is bound facially to Re through P and two of the phenoxy oxygens. The Ph(3)P group and terminal oxygen atoms are cis to the oxygen atoms of the phenoxy ligands and the Cl lies trans to P. One trimethylsiloxyphenol group dangles. Careful hydrolysis of 6 gave Re(O)Cl[kappa(3)-(P,O,O)-(P{O}(2){OH})](PPh(3)) which was also formed during complexation reactions in moist solvent. Solution (31)P{(1)H} NMR demonstrated cis- or trans-(P,P) geometry for the complexes, which was confirmed in the two aforementioned cases by structure determinations.

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“…To elucidate how molybdenum sites in these two enzymes participate in these relevant biological reactions, it is advantageous to explore the basic coordination chemistry of molybdenum, particularly, in a ligation environment similar to the enzymes. To this end, we utilize trisbenzenethiolatophosphines, PS3 and PS3 00 , as title ligands which were first developed by ZubietaÕs laboratory and have been investigated in other metal chemistry [1,[7][8][9][10][11][12][13][14][15][16]. In the reaction of molybdenum with these tetradentate ligands, two high valent molybdenum complexes, [Mo 2 (PS3) 2 (PS3H)] (1) and [Mo(PS3 00 ) 2 ] (2), were obtained.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and structural characterization of dimolybdenum(IV) and molybdenum(VI) complexes with trisbenzenethiolatophosphine ligands

Hsu

Peng

et al. 2005

Inorganica Chimica Acta

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Technetium(III) complexes with the tetradentate "umbrella" ligand tris(o-mercaptophenyl)phosphinate: x-ray structural characterization of Tc(P(o-C6H4S)3)(CNC3H7) and Tc(P(o-C6H4S)3)(CNC3H7)2

Cited by 43 publications

References 0 publications

Technetium Hydrides Revisited: Syntheses, Structures, and Reactions of [TcH₃(PPh₃)₄] and [TcH(CO)₃(PPh₃)₂]

Technetium Hydrides Revisited: Syntheses, Structures, and Reactions of [TcH₃(PPh₃)₄] and [TcH(CO)₃(PPh₃)₂]

Complexes of Multifunctional Phosphorus Ligands. Rhenium(V) Complexes of the Multidentate Phenoxyphosphine Ligands Bis(o-trimethylsilyloxyphenyl)phenylphosphine and Tris(o-trimethylsilyloxyphenyl)phosphine. Stepwise Elimination of Me₃SiX (X = Cl, OEt) from the Metal−Ligand System

Synthesis and structural characterization of dimolybdenum(IV) and molybdenum(VI) complexes with trisbenzenethiolatophosphine ligands

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Technetium(III) complexes with the tetradentate "umbrella" ligand tris(o-mercaptophenyl)phosphinate: x-ray structural characterization of Tc(P(o-C6H4S)3)(CNC3H7) and Tc(P(o-C6H4S)3)(CNC3H7)2

Cited by 43 publications

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Technetium Hydrides Revisited: Syntheses, Structures, and Reactions of [TcH3(PPh3)4] and [TcH(CO)3(PPh3)2]

Technetium Hydrides Revisited: Syntheses, Structures, and Reactions of [TcH3(PPh3)4] and [TcH(CO)3(PPh3)2]

Complexes of Multifunctional Phosphorus Ligands. Rhenium(V) Complexes of the Multidentate Phenoxyphosphine Ligands Bis(o-trimethylsilyloxyphenyl)phenylphosphine and Tris(o-trimethylsilyloxyphenyl)phosphine. Stepwise Elimination of Me3SiX (X = Cl, OEt) from the Metal−Ligand System

Synthesis and structural characterization of dimolybdenum(IV) and molybdenum(VI) complexes with trisbenzenethiolatophosphine ligands

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Technetium Hydrides Revisited: Syntheses, Structures, and Reactions of [TcH₃(PPh₃)₄] and [TcH(CO)₃(PPh₃)₂]

Technetium Hydrides Revisited: Syntheses, Structures, and Reactions of [TcH₃(PPh₃)₄] and [TcH(CO)₃(PPh₃)₂]

Complexes of Multifunctional Phosphorus Ligands. Rhenium(V) Complexes of the Multidentate Phenoxyphosphine Ligands Bis(o-trimethylsilyloxyphenyl)phenylphosphine and Tris(o-trimethylsilyloxyphenyl)phosphine. Stepwise Elimination of Me₃SiX (X = Cl, OEt) from the Metal−Ligand System