Coordination of Pnictogenylboranes Towards Tl(I) Salts and a Tl‐ Mediated P−P Coupling

Szlosek, Robert; Ackermann, Matthias T.; Marquardt, Christian; Seidl, Michael; Timoshkin, Alexey Y.; Scheer, Manfred

doi:10.1002/chem.202202911

Cited by 5 publications

(3 citation statements)

References 54 publications

(50 reference statements)

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“…[47]. This changed during the past two decades, in particular due to the use of weakly coordinating anions [48,49]. The fact that thallium(I) phosphine complexes are hardly accessible as long as there is an alternative for the metal cation is confirmed by the solid-state structure of compound 5.…”

Section: Transition Metal Complexesmentioning

confidence: 99%

Phosphine Functionalized CpC Ligands and Their Metal Complexes

Nährig¹,

Sun²,

Thiel³

2023

Chemistry

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Simple nucleophilic aliphatic substitution gives access to mono- and diphosphine ligands with a CpC group in the backbone. The monophosphine ligand coordinates to gold(I) via the phosphine site, to thallium(I) via the cyclopentadienyl site and to ruthenium(II) via a combination of both, resulting in an ansa-type structure. Coordination with the cyclopentadiene site is not possible for the diphosphine ligand. In this case, monodentate coordination to gold(I) and bidentate coordination to the [PdCl(μ2-Cl)]2, the [Rh(CO)(μ2-Cl)]2, and the Rh(CO)Cl fragment is observed, showing the variability in coordination modes possible for the long-chain diphosphine ligand. Ligands and complexes were characterized by means of NMR and IR spectroscopy, elemental analysis and X-ray structure analysis.

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Section: Transition Metal Complexesmentioning

confidence: 99%

Phosphine Functionalized CpC Ligands and Their Metal Complexes

Nährig¹,

Sun²,

Thiel³

2023

Chemistry

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“…Very recently, our group studied the coordination chemistry of pnictogenylboranes EH 2 BH 2 •NMe 3 (E = P, As) toward Tl I salts of different weakly coordinating anions (WCAs). 26 In terms of polyphosphorus ligand complexes, only few examples are known concerning the coordination chemistry toward thallium metal salts. For instance, the reaction of pentaphosphaferrocene [Cp*Fe(η 5 with Tl[TEF] in CH 2 Cl 2 delivered the dimeric compound [Tl 2 (η 1 -A) 4 (μ,η 1:1 -A) 2 ][TEF] 2 consisting of a distorted {Tl 2 P 4 } ring.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Since then, few examples have been published including Peter’s homoleptic phosphine adduct of Tl I , Power’s Tl 2 [Ar 2 P 4 ], , Bochmann’s Tl I arene or diethyl ether complexes. , Moreover, Mindiola and co-workers prepared PNP pincer complexes of Tl. Very recently, our group studied the coordination chemistry of pnictogenylboranes EH 2 BH 2 ·NMe 3 (E = P, As) toward Tl I salts of different weakly coordinating anions (WCAs) . In terms of polyphosphorus ligand complexes, only few examples are known concerning the coordination chemistry toward thallium metal salts.…”

Section: Introductionmentioning

confidence: 99%

Potential of Mixed Dipnictogen Molybdenum Complexes in the Self-Assembly of Thallium Coordination Compounds

Zimmermann,

Riesinger,

Scheer

2024

Inorg. Chem.

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The coordination chemistry of the homo-and heterodipnictogen tetrahedrane complexes [{CpMo-(CO) 2 } 2 (μ,η 2:2 -EE′)] (E, E′ = P, As, Sb) (A−F) toward Tl[BArF 24 ] ([BArF 24 ] − = [B(3,5-C 6 H 3 (CF 3 ) 2 ) 4 ] − ) was studied. Controlled by the used tetrahedranes A−F, and thus depending on the respective pnictogen atoms, the monomers [Tl(η 2 -A)][BArF 24 ] ([A]Tl) and [Tl(η 2 -B)][BArF 24 ] ([B]Tl), the double substituted6 Tl 2 ) were obtained. Utilization of [BArF 24 ] − promises additional stabilization of Tl I via η 6coordination of two of its aryl rings as found in compounds [A] Tl, [B]Tl and [C] 2 Tl. Within the series of reactivity of A−F, the heavier congeners D, E and F tend to form larger aggregates in which σ(E−E′) bond contributions to the coordination behavior were observed. Interatomic distances suggest the presence of Tl••• Tl interactions in [E] 5 Tl 2 and [F] 6 Tl 2 . The features of the respective coordination compounds were studied in the solid-state as well as in solution. For the latter at least a partial dissociation of the assemblies in solution was indicated. The isolated solid-state aggregates are the first examples of heterodipnictogen units as ligands in self-assembled Tl I -based coordination compounds.

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