Selective Formation of Gold(I) Bis-Phospholane Macrocycles, Polymeric Chains, and Nanotubes

Streitberger, Markus; Schmied, Andy; Hey‐Hawkins, Evamarie

doi:10.1021/ic5006055

Cited by 35 publications

(51 citation statements)

References 96 publications

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“…Hence, the Au···Cl interaction of complex 6 can be considered as merelye lectrostatic (NBO charges + 0.22 and À0.29 were computed for the Au and Cl atoms, respectively). [32] Therefore, all the above data clearly confirm that the PGeP germylene 1 is better suited to lead to PGeP pincer complexes than the only two previously known PGeP germylenes,n amely, Ge(NCH 2 PtBu 2 ) 2 C 6 H 4 and Ge(NC 6 H 4 PPh 2 ) 2 C 2 H 4 (A and B,r espectively,inF igure 1).…”

Section: 412supporting

confidence: 62%

A Germylene Supported by Two 2‐Pyrrolylphosphane Groups as Precursor to PGeP Pincer Square‐Planar Group 10 Metal(II) and T‐Shaped Gold(I) Complexes

Cabeza

Fernández

Fernández‐Colinas

et al. 2019

Chemistry A European J

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An efficient synthesis of 2-di-tert-butylphosphanylmethylpyrrole( HpyrmPtBu 2 ), by treating 2-dimethylaminomethylpyrrole( HpyrmNMe 2 )w ith tBu 2 PH at 135 8Ci nt he absence of any solvent,h as allowed the preparation of the new PGeP germyleneG e(pyrmPtBu 2 ) 2 (1), by treating [GeCl 2 (dioxane)] with LipyrmPtBu 2 ,i nw hich the Ge atom is stabilized by intramolecular interactions with one (solid state) or both (solution) of its phosphane groups.R eactions of germylene 1 with Group 10 metald ichlorido complexes containing easily displaceablel igandsh ave led to [MCl{k 3 P,Ge,P-GeCl(pyrmPtBu 2 ) 2 }] [M = Ni (2), Pd (3), Pt (4)], which have an unflawed square-planar metale nvironment.Treatmento fg ermylene 1 with [AuCl(tht)] (tht = tetrahydrothiophene) rendered[ Au{k 3 P,Ge,P-GeCl(pyrmPtBu 2 ) 2 }] (5), which is ar are case of aT -shaped gold(I) complex. The hydrolysis of 5 gave the linear gold(I) derivative [Au(kP-HpyrmPtBu 2 ) 2 ]Cl (6). Complexes 2-5 contain aP GeP pincer chloridogermyl ligandt hat arises from the insertionof the Ge atom of germylene 1 into aM ÀCl bond of the corresponding metal reagent. The bondingi nt hese molecules has been studied by DFT/NBO/QTAIM calculations. These results demonstrate that the great flexibility of germylene 1 makesi tabetter precursor to PGeP pincer complexes than the previouslyk nown germylenes of this type.[a] Prof.Supporting information (containingt he experimental details and analytical, spectroscopic, structural(XRD), and theoretical (DFT,QTAIM) and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Section: 412supporting

confidence: 62%

A Germylene Supported by Two 2‐Pyrrolylphosphane Groups as Precursor to PGeP Pincer Square‐Planar Group 10 Metal(II) and T‐Shaped Gold(I) Complexes

Cabeza

Fernández

Fernández‐Colinas

et al. 2019

Chemistry A European J

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“…The distortion occurs due to an additional, weak coordination of a terminal chlorido ligand. The Au-Cl bond 9 The cyclopentadienyl rings adopt a synperiplanar arrangement, and a gauche conformation is observed in analogy to 7a in one of the two alkylene spacers. Treatment of [{RhCl(CO) 2 } 2 ] with two equivalents of 5b in dichloromethane gave the corresponding complex [RhCl(CO)(5b-κ 2 P,P')] (9b).…”

Section: Scheme 2 Synthesis Of Metal Complexesmentioning

confidence: 99%

Heterobimetallic complexes with highly flexible 1,1′-bis(phospholanoalkyl)ferrocene ligands

et al. 2015

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The two highly flexible ligands 1,1'-bis(4-phospholanobutyl)ferrocene (5a) and 1,1'-bis(5-phospholanopentyl)ferrocene (5b) reacted with [PtCl2(cod)] (cod = 1,5-cyclooctadiene), [AuCl(tht)] (tht = tetrahydrothiophene) and [{RhCl(CO)2}2] to give the respective chelate complexes cis-[PtCl2(5a,b-κ(2)P,P')] (7a,b), [AuCl(5a,b-κ(2)P,P')] (8a,b) and trans-[RhCl(CO)(5b-κ(2)P,P')] (9b). Treatment of 5a,b with selenium gave the corresponding selenides 6a,b. All compounds have been fully characterised by NMR ((1)H, (13)C, (31)P) and IR spectroscopy and mass spectrometry. In addition, crystal structures of 6a, 7b, 8a,b and 9b were determined by X-ray crystallography. Furthermore, the rhodium-catalysed hydroformylation of 1-octene has been studied with ligand 5b.

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“…10 , 11 , 12 In contrast, when diphosphines with connectors consisting of three or more methylene units bridge two gold(I) centers, the gold ions are generally rather far apart. 13,14,15,16,17 With Ph 2 P(CH 2 ) 2 PPh 2 (dppe) and related ligands that utilize two methylene connectors, there is considerable flexibility in positioning two metal centers. For example, the dimers Au 2 (µ-dppe) 2 Br 2 and Au 2 (µ-dppe) 2 I 2 consist of two, three-coordinate P 2 AuX units.…”

Section: Introductionmentioning

confidence: 99%

Steric effects and aurophilic interactions in crystals of Au2(μ-1,2-bis(diphenylphosphino)ethane)X2 and Au2(μ-1,2-bis(dicyclohexylphosphino)ethane)X2 (X = Cl, Br, I)

et al. 2016

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Steric Effects and Aurophilic Interactions in Crystals of Au 2 (μ-1,2-bis(diphenylphosphino)ethane)X 2 and Au 2 (μ-1,2-bis(dicyclohexylphosphino)ethane)X 2 (X = Cl, Br, I), Polyhedron (2016), doi: http://dx. Abstract Crystalsin the isostructural series Au 2 (µ-dppe)X 2 (dppe is 1,2-bis(diphenylphosphino)ethane, X = Cl, Br, I) form centrosymmetric, dimeric structures with two short Au … Au contacts between the component molecules. We found no evidence for a second polymorph for any member of the Au 2 (µ-dppe)X 2 series, although two polymorphs were observed previously for the related Au 2 (Ph 2 As(CH 2 ) 2 AsPh 2 )X 2 series. Crystals of Au 2 (µ-dcpe)X 2 (where dcpe is 1,2-bis(dicyclohexylphosphino)ethane) show structures that differ appreciably from those of Au 2 (µ-dppe)X 2 . The bulky cyclohexyl substituents appear to be playing a major role eliminating the formation of polymeric or dimeric structures. Au 2 (µ-dcpe)Cl 2 has a monomeric structure without aurophilic interactions. In contrast, Au 2 (µ-dcpe)Br 2 and Au 2 (µ-dcpe)I 2 have similar structures with intramolecular aurophilic interactions. Au 2 (µ-dcpe)I 2 displays a form of aggregation-induced emission. It displays a red-pink luminescence in crystalline form but is non-emissive in solution.3

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Selective Formation of Gold(I) Bis-Phospholane Macrocycles, Polymeric Chains, and Nanotubes

Cited by 35 publications

References 96 publications

A Germylene Supported by Two 2‐Pyrrolylphosphane Groups as Precursor to PGeP Pincer Square‐Planar Group 10 Metal(II) and T‐Shaped Gold(I) Complexes

A Germylene Supported by Two 2‐Pyrrolylphosphane Groups as Precursor to PGeP Pincer Square‐Planar Group 10 Metal(II) and T‐Shaped Gold(I) Complexes

Heterobimetallic complexes with highly flexible 1,1′-bis(phospholanoalkyl)ferrocene ligands

Steric effects and aurophilic interactions in crystals of Au2(μ-1,2-bis(diphenylphosphino)ethane)X2 and Au2(μ-1,2-bis(dicyclohexylphosphino)ethane)X2 (X = Cl, Br, I)

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