Amido analogues of zincocenes and cadmocenes

Blake, Alexander J.; Lewis, William; McMaster, Jonathan; Moorhouse, Rhiannon S.; Moxey, Graeme J.; Kays, Deborah L.

doi:10.1039/c0dt01710h

Cited by 16 publications

(19 citation statements)

References 37 publications

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“…Compound 1 is a rare example of a crystallographically characterised terminal cadmium amide complex. Other examples include homoleptic complexes [Cd(TMP) 2 ] (TMP = 2,2,6,6‐tetramethylpiperidide) and [Cd( t Bu 4 carb) 2 ] ( t Bu 4 carb = 1,3,6,8‐tetra‐ tert ‐butylcarbazol‐9‐yl), the former of which was found to be active in cadmation reactions in the presence of [Li(TMP)] . Amide 1 was found to be a useful synthon in the synthesis of other low‐coordinate (β‐diketiminato)cadmium complexes (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

(β‐Diketiminato)cadmium Bis(trimethylsilyl)amide: Facile Access to Low‐Coordinate Cadmium Complexes

2016

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A new route to access low‐coordinate (β‐diketiminato)cadmium complexes has been developed. Treatment of [Cd(HMDS)2] with BDI‐H (HMDS = [N(SiMe3)2]; BDI = [{N(2,6‐iPr2C6H3)C(Me)}2CH]) forms [(BDI)Cd(HMDS)], which is a useful synthon for the generation of other low‐coordinate cadmium complexes such as anilido complex [(BDI)Cd(NH{N(2,6‐iPr2C6H3})(THF)], aryloxo complex [(BDI)Cd(O‐2,6‐tBu2C6H3)], as well as chloro complex [{(BDI)CdCl}2]. [(BDI)Cd(HMDS)] is extremely sensitive to hydrolysis, generating [{(BDI)Cd(OH)}2] upon exposure to “dry” tert‐butyl alcohol.

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Section: Resultsmentioning

confidence: 99%

(β‐Diketiminato)cadmium Bis(trimethylsilyl)amide: Facile Access to Low‐Coordinate Cadmium Complexes

2016

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“…74 As has been seen for the related cadmium complex (1,3,6,8-t Bu 4 carb) 2 Cd (82), 69 in 81 the two carbazolyl ligands lie parallel, but are rotated 1801 away from each other. 74 As has been seen for the related cadmium complex (1,3,6,8-t Bu 4 carb) 2 Cd (82), 69 in 81 the two carbazolyl ligands lie parallel, but are rotated 1801 away from each other.…”

Section: S-block Complexesmentioning

confidence: 77%

“…The molecular structures of [1,3,6,8-t Bu 4 carbLi] 2 (68) and 1,3,6,8-t Bu 4 carbNa(THF)3 (69) with thermal ellipsoids set at 50% 68. Hydrogen atoms are omitted for clarity.…”

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confidence: 99%

Extremely bulky amide ligands in main group chemistry

Kays

2016

Chem. Soc. Rev.

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The search for extremely sterically demanding monodentate amide ligands to access main group complexes in low-coordination numbers and highly reactive bonding modes is an area of intense research interest. The recent development of three classes of sterically demanding, monodentate amide ligands - the m-terphenyl anilides [N(R){C6H3Ar2-2,6}](-) (Ar = aryl, R = H, methyl, silyl), substituted carbazol-9-yl and the extremely bulky amides [N(R)(Ar')](-) (Ar' = 2,6-{C(H)Ph2}-4-R'-C6H2, R = silyl, aryl, silyloxy, R' = alkyl) is facilitating the isolation of stable species with new coordination modes for the main group elements. These compounds are of fundamental importance not only from the investigation of their structure and bonding, but also the investigation of their reactivity highlights the potential for small molecule activation chemistry under mild conditions and applications in catalysis. This review reports on the recent developments for these compounds with emphasis on their synthesis, structure and reactivity.

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“…In summary, the increased ability of 1 to allow approach of a metal centre in s fashion to N (1) [26] Experimental Section General details of synthetic procedures and instrumentation: Manipulations of air-sensitive reagents were carried out under a nitrogen or argon atmosphere using standard Schlenk line or dry-box techniques. Non-deuterated solvents were dried by using a commercially available Braun Solvent Purification System.…”

Section: Resultsmentioning

confidence: 99%

Tuning Main Group Redox Chemistry through Steric Loading: Subvalent Group 13 Metal Complexes of Carbazolyl Ligands

Mansaray

Kelly

Vidović

et al. 2011

Chemistry A European J

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The ability of substituted carbazol-9-yl systems to ligate in σ fashion through the amido N-donor, or to adopt alternative coordination modes through the π system of the central five-membered ring, can be tuned by systematic variation in the steric demands of substituents in the 1- and 8-positions. The differing affinities of the two modes of coordination for hard and soft metal centres can be shown to influence not only cation selectivity, but also the redox properties of the metal centre. Thus, the highly sterically sterically demanding 1,3,6,8-tetra-tert-butylcarbazolyl ligand can be used to generate the structurally characterised amido-indium(I) complex, [{(tBu(4)carb)In}(n)], (together with its isostructural thallium counterpart) in which the metal centre interacts with the central pyrrolyl ring in η(3) fashion [d(In-N)=2.679(3) Å; d(In-C)=2.819(3), 2.899(3) Å]. By contrast, the smaller 3,6-di-tert-butylcarbazolyl system is less able to restrict the metal centre from binding at the anionic nitrogen donor in the plane of the carbazolyl ligand (i.e. in σ fashion). Analogous chemistry with In(I) precursors therefore leads to disproportionation to the much harder In(II) [and In(0)], and the formation of the mixed-valence product, [In(2){In(2)(tBu(2)carb)(6)}], a homoleptic molecular [In(4)(NR(2))(6)] system. This chemistry reveals a flexibility of ligation for carbazolyl systems that contrasts markedly with that of the similarly sterically encumbered terphenyl ligand family.

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Amido analogues of zincocenes and cadmocenes

Cited by 16 publications

References 37 publications

(β‐Diketiminato)cadmium Bis(trimethylsilyl)amide: Facile Access to Low‐Coordinate Cadmium Complexes

(β‐Diketiminato)cadmium Bis(trimethylsilyl)amide: Facile Access to Low‐Coordinate Cadmium Complexes

Extremely bulky amide ligands in main group chemistry

Tuning Main Group Redox Chemistry through Steric Loading: Subvalent Group 13 Metal Complexes of Carbazolyl Ligands

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