Synthesis and structural characterization of trimethylphosphine complexes of technetium(III)

Watson, Patricia L.; Albanese, Joseph A.; Calabrese, Joseph C.; Ovenall, Derick W.; Smith, Richard G.

doi:10.1021/ic00024a035

Cited by 26 publications

(18 citation statements)

References 2 publications

(2 reference statements)

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“…The abstraction of the hydrides during such reactions comes not completely unexpected and the reformation of [TcCl 4 (PPh 3 ) 2 ] from the hydrido complex 1 in chlorinated hydrocarbon solvents has been observed before . The structure of [TcCl 3 (PMe 3 ) 3 ] with cocrystallized OPPh 3 is similar to that reported for [TcCl 3 (PMe 3 ) 3 ]·(PhNCO) 3 . Details are discussed in the Supporting Information.…”

Section: Resultssupporting

confidence: 64%

“…In contrast to the coordination chemistry of its higher congener rhenium, where many hydrido complexes are known and play an important role in a number of catalytic processes, − reports about compounds with technetium–hydrogen bonds are scarce. − Only some of them have been characterized unambiguously, e.g., by single crystal X-ray crystallography. This includes mononuclear compounds such as [TcH(N 2 )(dppe) 2 ], [TcH{η 2 - N , S -HNC(NH 2 )S}(PMe 3 ) 4 ](PF 6 ), or [Tc(H 2 )Cl(dppe) 2 ], the binuclear compound [Tc 2 -μ-H(μ- C , N -C 5 H 4 N)(py) 2 (CO) 6 ], but also the trinuclear clusters [Tc 3 -μ-H 3 (CO) 12 ] , and [Tc 3 H(CO) 14 ] or some borohydride compounds. , The structure of the iconic K 2 [TcH 9 ] was determined by comparison of its powder data with those of the rhenium analogue . Some of the compounds are shown in Chart .…”

Section: Introductionmentioning

confidence: 99%

“…8−23 Only some of them have been characterized unambiguously, e.g., by single crystal X-ray crystallography. This includes mononuclear compounds such as [TcH(N 2 )(dppe) 2 ], 13 [TcH{η 2 -N,S-HNC(NH 2 )S}-(PMe 3 ) 4 ](PF 6 ), 15 or [Tc(H 2 )Cl(dppe) 2 ], 16 the binuclear compound [Tc 2 -μ-H(μ-C,N-C 5 H 4 N)(py) 2 (CO) 6 ], 19 but also the trinuclear clusters [Tc 3 -μ-H 3 (CO) 12 ] 18,21 and [Tc 3 H-(CO) 14 ] 20 or some borohydride compounds. 22,23 The structure of the iconic K 2 [TcH 9 ] was determined by comparison of its powder data with those of the rhenium analogue.…”

Section: ■ Introductionmentioning

confidence: 99%

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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: Resultssupporting

confidence: 64%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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

2021

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“…When considering tautomerism and TU interaction with Lewis acids, resonance structures (Scheme 1, right-hand side) rationalize the stability of TM complexes with both the C-Sand the -NHfunctional groups coordinated (e.g. Watson et al, 1991;Fritz et al, 1994;Seitz et al, 1994).…”

Section: Introductionmentioning

confidence: 99%

Ground electronic state description of thiourea coordination in homoleptic Zn²⁺, Ni²⁺ and Co²⁺ complexes using sulfur K-edge X-ray absorption spectroscopy

Queen¹,

Jalilehvand²,

Szilágyi³

2021

J Synchrotron Radiat

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Sulfur K-edge X-ray absorption spectroscopy (XAS) was employed to experimentally characterize the coordinative bond between the thiourea (TU) or thiocarbamide ligand and transition metal (TM) ions Zn2+, Co2+ and Ni2+ in distorted tetrahedral and octahedral homoleptic coordination environments. Comparisons of XAS spectra of the free TU ligand and [Zn(TU)4]2+, [Co(TU)4]2+ and [Ni(TU)6]2+ complexes clearly identify spectral features unique to TM2+–S(TU) bonding. Quantitative analysis of pre-edge intensities describes the covalency of Ni2+—S(TU) and Co2+—S(TU) bonding to be at most 21% and 9% as expressed by the S 3p contributions per TM 3d electron hole. Using relevant Ni2+ complexes with dithiocarbamate and thioether ligands, we evaluated the empirical S 1s → 3p transition dipole integrals developed for S-donor ligands and their dependence on heteroatom substitutions. With the aid of density functional theory-based ground electronic state calculations, we found evidence for the need of using a transition dipole that is dependent on the presence of conjugated heteroatom (N) substitution in these S-donor ligands.

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“…Organosulfur compounds play an important role in modern organic synthesis, not only because they constitute a particularly useful class of synthons [16] but also because they are of great biological interest [17–23] such as fungicidal [24], bactericidal [25–27], insecticidal [28], and antitumor agents for thioureidoalkanethiourea [29–32]. Symmetrical and unsymmetrical 2,5‐dithiobiureas have been utilized widely in the synthesis of heterocylic compounds and are considered as very good complexing agents for a variety of materials in the synthesis of complexes [33–39]. Substituted‐2,5‐dithiobiureas and their derivatives are versatile compounds, which have been extensively used in the preparation of heterocyclic ring systems.…”

Section: Introductionmentioning

confidence: 99%

Chemistry and heterocyclization of dithiobiurea and thioureidoalkylthiourea

Hassan

El‐Sheref

2010

Journal of Heterocyclic Chem

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Synthesis and structural characterization of trimethylphosphine complexes of technetium(III)

Cited by 26 publications

References 2 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]

Ground electronic state description of thiourea coordination in homoleptic Zn²⁺, Ni²⁺ and Co²⁺ complexes using sulfur K-edge X-ray absorption spectroscopy

Chemistry and heterocyclization of dithiobiurea and thioureidoalkylthiourea

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Synthesis and structural characterization of trimethylphosphine complexes of technetium(III)

Cited by 26 publications

References 2 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]

Ground electronic state description of thiourea coordination in homoleptic Zn2+, Ni2+ and Co2+ complexes using sulfur K-edge X-ray absorption spectroscopy

Chemistry and heterocyclization of dithiobiurea and thioureidoalkylthiourea

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Resources

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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]

Ground electronic state description of thiourea coordination in homoleptic Zn²⁺, Ni²⁺ and Co²⁺ complexes using sulfur K-edge X-ray absorption spectroscopy