Hauptgruppenmetallcluster stabilisiert durch N‐heterocyclische Carbene

Wolf, Robert; Uhl, Werner

doi:10.1002/ange.200902287

Cited by 23 publications

(7 citation statements)

References 49 publications

(21 reference statements)

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“…The reaction was then filtered through Celite and the volatiles were removed in vacuo to yield [D 2 ]-8 as a bright-yellow oil (57 mg, 79 % yield). 1 H NMR (500 MHz, C 6 D 6 ): essentially the same as compound 8 except for the absence of a resonance for the -CH 2 -group at d = 3.17 ppm; 2 H{ 1 H} NMR (61 MHz, C 6 H 6 ): d = 3.16 ppm (-CD 2 -).…”

Section: Thermolysismentioning

confidence: 96%

“…The minor (20 %) orientation of the disordered diisopropylphenyl group in molecule B was restrained to have the same geometry as that of the major orientation by use of the SHELXL SAME instruction. The disordered solvent (diethyl ether) molecule had the following restraints applied: CÀC 1.53(1) ; CÀO 1.43(1) ; CÀO 2.42(1) ; CÀC 2.34 (1) . Finally, the following pairs of atoms were restrained to have equivalent anisotropic displacement parameters: C51A/C, C52A/C, C53A/C, C54A/C, C55A/C, C56A/C, C62A/C, B1A/C, and O1S/O2S.…”

Section: Special Refinement Conditionsmentioning

confidence: 99%

“…The use of electron-donating N-heterocyclic carbenes (NHCs) to stabilize reactive main-group species is a rapidly expanding area of inorganic chemistry. [1] In many instances, the resulting coordinative NHC-element interactions are of sufficient strength to enable the isolation of complexes featuring molecular entities that only exist as fleeting intermediates or were previously unknown altogether. For example, the recent isolation of stable molecular adducts of the parent compounds borylene (DBH) [2] and disilylene (DSi=SiD) [3] represents a synthetic breakthrough made possible by carbene coordination chemistry.…”

Section: Introductionmentioning

confidence: 99%

“…M.p. 179-181 8C;1 H NMR (500 MHz, C 6 D 6 ): d = 0.96 (d, 3 J HH = 7.0 Hz, 6 H; CHA C H T U N G T R E N N U N G (CH 3 ) 2 ), 1.02 (d, 3 J HH = 7.0 Hz, 6 H; CHA C H T U N G T R E N N U N G (CH 3 ) 2 ), 1.14 (d, 3 J HH = 7.0 Hz, 6 H; CHA C H T U N G T R E N N U N G (CH 3 ) 2 ), 1.27 (d, 3 J HH = 7.0 Hz, 6 H; CHA C H T U N G T R E N N U N G (CH 3 ) 2 ), 1.34 (d, 3 J HH = 7.0 Hz, 6 H; CH-A C H T U N G T R E N N U N G (CH 3 ) 2 ), 1.48 (d, 3 J HH = 7.0 Hz, 6 H; CHA C H T U N G T R E N N U N G (CH 3 ) 2 ), 2.96 (septet, 3 J HH = 7.0 Hz, 4 H; CHA C H T U N G T R E N N U N G (CH 3 ) 2 ), 3.20 (septet, 3 J HH = 7.0 Hz, 2 H; CHA C H T U N G T R E N N U N G (CH 3 ) 2 ), 4.14 (s, 1 H; -NH), 6.36 (s, 2 H; NCH-), 6.94 (t, 3 J HH = 7.5 Hz, 1 H; ArH), 6.99-7.19 ppm (m, 8 H; ArH); 13 C{ 1 H} NMR (125 MHz, C 6 D 6 ): d = 22.9 (CH-A C H T U N G T R E N N U N G (CH 3 ) 2 ), 23.1 (CHA C H T U N G T R E N N U N G (CH 3 ) 2 ), 24.8 (CHA C H T U N G T R E N N U N G (CH 3 ) 2 ), 25.2 (CHA C H T U N G T R E N N U N G (CH 3 ) 2 ), 25.8 (CH-A C H T U N G T R E N N U N G (CH 3 ) 2 ), 25.9 (CHA C H T U N G T R E N N U N G (CH 3 ) 2 ), 27.8 (CHA C H T U N G T R E N N U N G (CH 3 ) 2 ), 28.8 (CHA C H T U N G T R E N N U N G (CH 3 ) 2 ), 29.5 (CH-A C H T U N G T R E N N U N G (CH 3 ) 2 ),121.3 (ArC), 123.7 (ArC), 123.9 (ArC), 124.3 (ArC), 124.5 (-NCH-), 131.4 (ArC), 133.7 (ArC), 140.5 (ArC), 141.9 (ArC), 145.8 (ArC), 146.3 (ArC), 171.7 ppm (NCN); 29 Si NMR (80 MHz, C 6 D 6 ): d = À6.0 ppm; IR (Nujol): ñ = 3360 cm À1 (s, NÀH); elemental analysis calcd (%) for C 39 H 54 ClN 3 Si: C 74.54, H 8.66, N 6.69; found: C 74.54, H 8.49, N 6.58. IPr·Ge(Cl)NHDipp (2): A solution of LiA C H T U N G T R E N N U N G [NHDipp] (0.18 g, 0.98 mmol) in cold Et 2 O (12 mL, À35 8C) was added dropwise to a cold (À35 8C) slurry of IPr·GeCl 2 (0.51 g, 0.96 mmol) in Et 2 O (5 mL).…”

mentioning

confidence: 99%

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Preparation of Stable Low‐Oxidation‐State Group 14 Element Amidohydrides and Hydride‐Mediated Ring‐Expansion Chemistry of N‐Heterocyclic Carbenes

Al‐Rafia

McDonald

Ferguson

et al. 2012

Chemistry A European J

141

115

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Various low oxidation state (+2) group 14 element amidohydride adducts, IPr⋅EH(BH(3))NHDipp (E=Si or Ge; IPr=[(HCNDipp)(2)C:], Dipp=2,6-iPr(2)C(6)H(3)), were synthesized. Thermolysis of the reported adducts was investigated as a potential route to Si- and Ge-based clusters; however, unexpected transmetallation chemistry occurred to yield the carbene-borane adduct, IPr⋅BH(2)NHDipp. When a solution of IPr⋅BH(2)NHDipp in toluene was heated to 100 °C, a rare C-N bond-activation/ring-expansion reaction involving the bound N-heterocyclic carbene donor (IPr) transpired.

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Section: Thermolysismentioning

confidence: 96%

Section: Special Refinement Conditionsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Preparation of Stable Low‐Oxidation‐State Group 14 Element Amidohydrides and Hydride‐Mediated Ring‐Expansion Chemistry of N‐Heterocyclic Carbenes

Al‐Rafia

McDonald

Ferguson

et al. 2012

Chemistry A European J

141

115

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“…We recently demonstrated that NHCs can effectively stabilize highly reactive molecules. [14][15][16][17] Prominent examples of carbene-stabilized complexes not only include diphosphorus, [6] diborenes ([LD(H)B=B(H)DL]), [18,19] and disilicon ([LDSi=SiDL]), [20] but this strategy also succeeded in the recent preparation of a neutral metalloaromatic Ga 6 octahedron ([LDGaA C H T U N G T R E N N U N G (Ga 4 Mes 4 )GaDL]). [21] Herein, we now report the syntheses, X-ray structures, and computations of carbenestabilized arsenic derivatives of AsCl 3 ([L 1…”

mentioning

confidence: 99%

Carbene Stabilization of Diarsenic: From Hypervalency to Allotropy

Abraham¹,

Wang²,

Xie³

et al. 2009

Chemistry A European J

198

160

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In contrast to nitrogen, the lightest yet most ubiquitous Group 15 element, phosphorus and arsenic exhibit extensive allotropy. Along with the more stable polymeric forms, both white phosphorus and yellow arsenic are well-known tetrahedral allotropes. Indeed, P 4 and As 4 readily pyrolyze to afford P 2[1] and As 2 , [2,3] respectively, which are well-characterized energetically and spectroscopically in the gas phase, [4] but are only persistent at high temperatures. Cummins and co-workers demonstrated that it is possible to generate complexes of diphosphorus in condensed phases by mild thermal extrusion of P 2 from niobium diphosphaazide complexes.[5] We subsequently reported a new class of carbene-stabilized diphosphorus molecules, [LDPÀPDL] (LD = Nheterocyclic carbenes (NHCs)).[6] Most recently, Bertrand and co-workers synthesized cyclicA C H T U N G T R E N N U N G (alkyl)A C H T U N G T R E N N U N G (amino)carbene-stabilized P 1 and P 2 complexes by P 4 fragmentation. [7] The bond energy of N 2 (226 kcal mol À1) is nearly twice that of P 2 (116 kcal mol À1 ) [8] and thrice that of As 2 (83 kcal mol À1 ), [9] thus suggesting a diminished importance of p-p bonding among third and fourth period elements. [10] Consequently, unlike N 2 , which usually [11] exhibits bonding mode A (Scheme 1) in its complexes, the E 2 cores in the corresponding diphosphorus and diarsenic complexes may assume either bonding mode A (triply bonded dipnictogen) or B (singly bonded dipnictinidene; Scheme 1). For example, diarsenic, like diphosphorus, has been known to function as a four-, six-, or eight-electron-donor ligand (C-G, Scheme 1) in transition-metal (M)-carbonyl complexes.[1, 2, 12, 13] An E 2 (E = P or As) fragment with an A-type structure may be extracted from C-F, [1] whereas the dipnictinidene core (B) has been observed in G. [2,13] Is it possible to prepare a carbenestabilized diarsenic analogue of H (Scheme 1)?We recently demonstrated that NHCs can effectively stabilize highly reactive molecules. [14][15][16][17] Prominent examples of carbene-stabilized complexes not only include diphosphorus, [6] [18,19] and disilicon ([LDSi=SiDL]), [20] but this strategy also succeeded in the recent preparation of a neutral metalloaromatic Ga 6 octahedron ([LDGaA C H T U N G T R E N N U N G (Ga 4 Mes 4 )GaDL]). diborenes ([LD(H)B=B(H)DL]),[21] Herein, we now report the syntheses, X-ray structures, and computations of carbenestabilized arsenic derivatives of AsCl 3 ([L The hypervalent carbene-stabilized arsenic chloride compound 1 was prepared, in nearly quantitative yield, by the treatment of AsCl 3 with the carbene ligand (L 1 D) [22] (Scheme 2). Subsequent potassium/graphite reduction of 1 affords the carbene-stabilized diarsenic complex, 2, as airsensitive red crystals (Scheme 2

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Al₁₂K₈[OC(CH₃)₃]₁₈: A Wade, Zintl, or Metalloid Cluster, or a Hybrid of All Three?

et al. 2010

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Hauptgruppenmetallcluster stabilisiert durch N‐heterocyclische Carbene

Cited by 23 publications

References 49 publications

Preparation of Stable Low‐Oxidation‐State Group 14 Element Amidohydrides and Hydride‐Mediated Ring‐Expansion Chemistry of N‐Heterocyclic Carbenes

Preparation of Stable Low‐Oxidation‐State Group 14 Element Amidohydrides and Hydride‐Mediated Ring‐Expansion Chemistry of N‐Heterocyclic Carbenes

Carbene Stabilization of Diarsenic: From Hypervalency to Allotropy

Al₁₂K₈[OC(CH₃)₃]₁₈: A Wade, Zintl, or Metalloid Cluster, or a Hybrid of All Three?

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Hauptgruppenmetallcluster stabilisiert durch N‐heterocyclische Carbene

Cited by 23 publications

References 49 publications

Preparation of Stable Low‐Oxidation‐State Group 14 Element Amidohydrides and Hydride‐Mediated Ring‐Expansion Chemistry of N‐Heterocyclic Carbenes

Preparation of Stable Low‐Oxidation‐State Group 14 Element Amidohydrides and Hydride‐Mediated Ring‐Expansion Chemistry of N‐Heterocyclic Carbenes

Carbene Stabilization of Diarsenic: From Hypervalency to Allotropy

Al12K8[OC(CH3)3]18: A Wade, Zintl, or Metalloid Cluster, or a Hybrid of All Three?

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Al₁₂K₈[OC(CH₃)₃]₁₈: A Wade, Zintl, or Metalloid Cluster, or a Hybrid of All Three?