Cobalt, Rhodium, Iridium, and Ruthenium Carbonyl Complexes with Stanna-closo-dodecaborate:103Rh NMR,119Sn Mössbauer Spectroscopy, and Solid-State119Sn NMR

Fleischhauer, Sebastian; Eichele, Klaus; Schellenberg, Inga; Pöttgen, Rainer; Wesemann, Lars

doi:10.1021/om200301v

Cited by 12 publications

(8 citation statements)

References 94 publications

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“…The pincer ligand is coordinated in a meridional arrangement, and the tin ligand is in a position trans to the carbon ligand of the pincer moiety. The Rh–Sn distance is comparable with those of other stanna- closo -dodecaborate complexes of rhodium …”

Section: Results and Discusssionsupporting

confidence: 72%

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Different Coordination Modes of the Ph₂PC_sp³PPh₂ Pincer Ligand in Rhodium Complexes as a Consequence of C_sp³–H Metal Interaction

et al. 2015

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Starting from commercially available 4,4′-di-tert-butyldiphenylmethane the pincer ligand bis(4-tert-butyl-2-(diphenylphosphino)phenyl)methane (PCP) was prepared in two steps in moderate yield. Treatment of a solution of RhCl3·3H2O in a mixture of isopropyl alcohol and toluene with equimolar amounts of PCP gave the dimeric rhodium complex 1. In an electrophilic metalation a facially coordinated pincer complex is formed. When PCP is treated with [CODRhCl]2 in a solution of pyridine, the square-pyramidal complex 2 is generated where the bis-phosphine PCP acts as bidentate ligand that coordinates in a cis fashion. SnCl2 inserts into the Rh–Cl bond of 2, which results in an oxidative addition of one of the methylene C–H bonds to form the Rh(III) complex 3, where the PCP ligand coordinates in a meridional way. A 2 equiv portion of PCP reacts with 1 equiv of [CODRhCl]2 in the presence of the electron-donating ligands HPhPC6H4NMe2, PPh2Py, and PPh3, respectively, as well as with stanna- and germa-closo-dodecaborate to give the octahedral Rh(III) complexes 4–8. Attempts to remove the HCl with KOtBu from complexes 4–6 produces the planar Rh(I) compounds 9 and 10. No carbene formation has been observed.

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Section: Results and Discusssionsupporting

confidence: 72%

“…The Rh−Sn distance is comparable with those of other stanna-closo-dodecaborate complexes of rhodium. 66…”

Section: ■ Results and Discusssionmentioning

confidence: 99%

Different Coordination Modes of the Ph₂PC_sp³PPh₂ Pincer Ligand in Rhodium Complexes as a Consequence of C_sp³–H Metal Interaction

et al. 2015

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“…These vibrations point toward less back‐bonding character of the carbonyl ligands, and therefore, weak donation of the P–Sn ligand. [14a], A characteristic feature of the rhodium complex 7 in the 119 Sn{ 1 H} NMR spectrum is a broad 119 Sn NMR spectroscopic signal at δ = –359 ppm, indicating coordination of the tin ligand. Two signals in the 31 P{ 1 H} NMR spectrum at δ = 19.8 ppm, which exhibits coupling with the 103 Rh nucleus of 119 Hz and the 119/117 Sn nuclei of 420 Hz, and a broad resonance at δ = 11.2 ppm for the B–P unit, are detected.…”

Section: Resultsmentioning

confidence: 99%

“…In this dimer (Figure ), one rhodium atom is coordinated by two heteroborates through the tin‐donor site, with distances close to literature values for P–Sn ligands and complex 7 . [14a], , The other rhodium atom is coordinated by two B–H units of a borate. This type of coordination is well known in boron‐cluster coordination chemistry, and here, two B–H units act as a bidentate ligand .…”

Section: Resultsmentioning

confidence: 99%

“…Phenyl groups of the xantphos moiety, except for their ipso carbon atoms, are omitted for the sake of clarity. Selected interatomic distances [Å] and angles [°]: Rh1-Sn1 2.6314(2), Rh1-Sn2 2.5625(2), Rh1-P1 2.2878(6), Rh1-C1 1.843(2), C1-O1 1.145 (3), Rh2-P3 2.2373(6), Rh2-C2 1.835(2), C2-O2 1.139 (3), Rh2-B23 2.399(1), Rh2-B27 2.348(1), P2-B2 1.936 (3), P4-B22 1.953(2), Sn1-Rh1-Sn2 88.431 (7), Sn1-Rh1-P1 96.691 (15), Sn1-Rh1-C1 172.47 (7), Sn2-Rh1-P1 171.291(17), Sn2-Rh1-C1 84.15 (7), P1-Rh1-C1 90.83 (7), P3-Rh2-C2 90.72 (7).…”

Section: Complexation Of the Anionic P-sn Ligand Of Saltmentioning

confidence: 99%

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Synthesis and Coordination Chemistry of a Chelating P–Sn Ligand Based on Stanna‐closo‐dodecaborate

2017

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Synthese von Cobalt‐Zinn‐ und ‐Blei‐Tetrylidinen – Reaktivitätsuntersuchungen der Dreifachbindung

Auer,

Zwettler,

Eichele

et al. 2023

Angewandte Chemie

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Die Tetrylidine [TbbSn≡Co(PMe3)3] (1 a) und [TbbPb≡Co(PMe3)3] (2) (Tbb=2,6‐[CH(SiMe3)2]2‐4‐(t‐Bu)C6H2) wurden über eine Substitutionsreaktion zwischen [Na(OEt2)][Co(PMe3)4] und [Li(thf)2][TbbEBr2] (E=Sn, Pb) erstmals dargestellt. Alternativ wurde das Stannylidin [Ar*Sn≡Co(PMe3)3] (1 b) durch eine Wasserstoffatom‐Abstraktion am paramagnetischen Hydridkomplex [Ar*SnH=Co(PMe3)3] (4) in einer Reaktion mit AIBN (AIBN=Azobis(iso‐butyronitril)) synthetisiert. Das Stannylidin 1 a addiert zwei Äquivalente Wasser, wobei das Dihydroxid [TbbSn(OH)2CoH2(PMe3)3] (5) erhalten wird. Bei der Reaktion des Stannylidins 1 a mit CO2 wurde ein Produkt einer Redoxreaktion [TbbSn(CO3)Co(CO)(PMe3)3] (6) isoliert. Die Protonierung des Tetrylidins erfolgt am Cobaltatom und ergibt das Metallastannavinyl‐Kation [TbbSn=CoH(PMe3)3][BArF4] (7 a) [ArF=C6H3‐3,5‐(CF3)2]. Die analogen Germanium‐ und Zinnkationen [Ar*E=CoH(PMe3)3][BArF4] (E=Ge 9, Sn 7 b) (Ar*=C6H3(2,6‐Trip)2, Trip=2,4,6‐C6H2iPr3) wurden durch Oxidation der paramagnetischen Komplexe [Ar*EH=Co(PMe3)3] (E=Ge 3, Sn 4) ebenfalls erhalten, welche durch Substitution eines PMe3‐Liganden am [Co(PMe3)4]‐Komplex durch eine Hydridoylen‐Einheit (Ar*EH) synthetisiert werden können.

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Cobalt, Rhodium, Iridium, and Ruthenium Carbonyl Complexes with Stanna-closo-dodecaborate:¹⁰³Rh NMR,¹¹⁹Sn Mössbauer Spectroscopy, and Solid-State¹¹⁹Sn NMR

Cited by 12 publications

References 94 publications

Different Coordination Modes of the Ph₂PC_sp³PPh₂ Pincer Ligand in Rhodium Complexes as a Consequence of C_sp³–H Metal Interaction

Different Coordination Modes of the Ph₂PC_sp³PPh₂ Pincer Ligand in Rhodium Complexes as a Consequence of C_sp³–H Metal Interaction

Synthesis and Coordination Chemistry of a Chelating P–Sn Ligand Based on Stanna‐closo‐dodecaborate

Synthese von Cobalt‐Zinn‐ und ‐Blei‐Tetrylidinen – Reaktivitätsuntersuchungen der Dreifachbindung

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Cobalt, Rhodium, Iridium, and Ruthenium Carbonyl Complexes with Stanna-closo-dodecaborate:103Rh NMR,119Sn Mössbauer Spectroscopy, and Solid-State119Sn NMR

Cited by 12 publications

References 94 publications

Different Coordination Modes of the Ph2PCsp3PPh2 Pincer Ligand in Rhodium Complexes as a Consequence of Csp3–H Metal Interaction

Different Coordination Modes of the Ph2PCsp3PPh2 Pincer Ligand in Rhodium Complexes as a Consequence of Csp3–H Metal Interaction

Synthesis and Coordination Chemistry of a Chelating P–Sn Ligand Based on Stanna‐closo‐dodecaborate

Synthese von Cobalt‐Zinn‐ und ‐Blei‐Tetrylidinen – Reaktivitätsuntersuchungen der Dreifachbindung

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Product

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Cobalt, Rhodium, Iridium, and Ruthenium Carbonyl Complexes with Stanna-closo-dodecaborate:¹⁰³Rh NMR,¹¹⁹Sn Mössbauer Spectroscopy, and Solid-State¹¹⁹Sn NMR

Different Coordination Modes of the Ph₂PC_sp³PPh₂ Pincer Ligand in Rhodium Complexes as a Consequence of C_sp³–H Metal Interaction

Different Coordination Modes of the Ph₂PC_sp³PPh₂ Pincer Ligand in Rhodium Complexes as a Consequence of C_sp³–H Metal Interaction