Reactions of the [Ni6(CO)12]2- dianion with stibine and bismuthine reagents: synthesis and stereophysical characterization of the [Ni10(SbPh)2(CO)18]2- dianion containing a noncentered icosahedral Ni10Sb2 core and Ni2(CO)4(μ2-Ph2SbOSbPh2)2 containing a centrosymmetric eight-membered (NiSbOSb)2 ring

DesEnfants, Robert E.; Gavney, James A.; Hayashi, Randy K.; Rae, A. D.; Dahl, Lawrence F.; Bjarnason, Ásgeir

doi:10.1016/0022-328x(90)85153-p

Cited by 41 publications

(26 citation statements)

References 37 publications

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“…50 %) (Scheme 1). This behavior is in contrast to the previous reports that described the potential of some (R 2 Sb) 2 E chalcogenides to act as terminal [15] or bridging [15][16][17][18] ligands in transition-metal complexes. The compounds were obtained as air-stable, colorless (3, 4), yellow (5), or orange (6) crystalline solids that melt without decomposition.…”

Section: Resultscontrasting

confidence: 84%

Synthesis and Characterization of Hypervalent Organoantimony(III) Compounds Containing the [2‐(Me₂NCH₂)C₆H₄]₂Sb Fragment

et al. 2009

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Compounds containing the [2‐(Me2NCH2)C6H4]2Sb moiety were prepared by using R2SbX [X = Cl (1), Br (2)] as starting materials. The reaction of 1 with Me3SiCH2MgCl gave the mixed alkyl–aryl stibine R2SbCH2SiMe3 (3). Reduction of 2 with Mg in thf followed by in situ air oxidation or treatment with S8 resulted in the isolation of (R2Sb)2E [E = O (4), S (5)]. Compound 5 is also formed from R2SbCl and Na2S. The reaction of 4 with [W(CO)5(thf)] gives the unexpected complex [(R2SbOH)W(CO)5] (6). The new compounds were investigated by IR, 1H, and 13C NMR spectroscopy, as well as by mass spectrometry. The structures of 3–6 were determined by single‐crystal X‐ray diffraction. For compounds 3–5, both nitrogen atoms from the pendant arms are involved in intramolecular N→Sb coordination, which results in distorted square‐pyramidal (C,N)2SbC or (C,N)2SbE (E = O, S) cores. By contrast, in 6 only one nitrogen atom is strongly coordinated to the antimony center, whereas the second nitrogen atom is involved in N···H–O bonding. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Section: Resultscontrasting

confidence: 84%

Synthesis and Characterization of Hypervalent Organoantimony(III) Compounds Containing the [2‐(Me₂NCH₂)C₆H₄]₂Sb Fragment

et al. 2009

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“…This assignment was corroborated by a single-crystal diffraction study ( Figure 1). [4] In the solid-state structure of 1, the nickel center adopts a distorted tetrahedral geometry with large P-Ni-P angles, the sum of which is equal to 348.75(15)8. As a result of the constraints enforced by the ligand backbone, the four coordinate antimony center also displays an unusual geometry characterized by a large Ni-Sb-C angle of 159.77(11)8.…”

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confidence: 99%

“…The Ni-Sb distance of 2.4574(10) in 1 is comparable to the average Ni-Sb distance of 2.449(2) in Ni 2 (CO) 4 (m 2 -Ph 2 SbOSbPh 2 ) 2 , one of the few structurally characterized arylstibine complexes of zerovalent nickel. [5] With compound 1 in hand, we sought to determine whether the Sb-Ni heterobimetallic core could sustain oxidation without decomposition. Gratifyingly, 1 undergoes a clean, two-electron oxidation by PhICl 2 in toluene to afford the dark purple complex 2 characterized by a single 31 P NMR resonance at 35.42 ppm in CDCl 3 (Scheme 1).…”

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confidence: 99%

“…An X-ray diffraction study revealed that 2 is a Sb-Ni lantern complex with a Sb-Ni distance (2.4852(5) ) almost identical to that in 1. [4] In contrast to 1 however, the nickel atom adopts a trigonal bipyramidal geometry with the antimony atom and a chloride ligand at the axial positions. The three equatorial positions are occupied by the phosphine arms of the L ligand (AE](P-Ni-P) = 357.97(12)8; Figure 1).…”

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Redox and Anion Exchange Chemistry of a Stibine–Nickel Complex: Writing the L, X, Z Ligand Alphabet with a Single Element

2014

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According to the covalent bond classification (CBC) method, two-electron donors are defined as L-type ligands, one-electron donors as X-type ligands, and two-electron acceptors as Z-type ligands. These three ligand functions are usually associated to the nature of the ligating atom, with phosphine, alkyl, and borane groups being prototypical examples of L-, X- and Z-ligands, respectively. A new SbNi platform is reported in which the ligating Sb atom can assume all three CBC ligand functions. Using both experimental and computational data, it is shown that PhICl2 oxidation of (o-(Ph2P)C6H4)3SbNi(PPh3) (1) into [(o-(Ph2P)C6H4)3ClSb]NiCl (2) is accompanied by a conversion of the stibine L-type ligand of 1 into a stiboranyl X-type ligand in 2. Furthermore, the reaction of 2 with the catecholate dianion in the presence of cyclohexyl isocyanide results in the formation of [(o-(Ph2P)C6H4)3(o-O2C6H4Sb)]Ni(CNCy) (4), a complex featuring a nickel atom coordinated by a Lewis acidic, Z-type, stiborane ligand.

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“…Furthermore, when in cyclic complexes such as ([l 2 -(H 5 C 6 ) 2 Sb±O±Sb-(C 6 H 5 ) 2 ]L n M) 2 (L n M = (OC) 4 Cr [23], (OC) 2 Ni [24]) the antimony atoms of this compound are coordinated to transition metal carbonyl fragments, a slight but significant shortening of the mean Sb±O distance from 197.1 to 195.5 and 194.3 pm, respectively, is ascertained. Since the same observation has been reported recently for the analogous bis(dimethylstibanyl)oxane complex ([l 2 -(Me 2 Sb±O±SbMe 2 )](OC) 4 Cr) 2 (198.8 to 195.3 pm [20]), we assume that the shift of electron density from antimony to the metal atom enhances the positive charge at the pnicogen atom so that in spite of its now higher coordination number the length of the a priori polar Sb±O bond decreases.…”

Section: Resultsmentioning

confidence: 99%

Common Features in the Crystal Structures of the Compounds Bis(dimethylstibanyl)oxane and -sulfane, and the Minerals Valentinite and Stibnite (Grauspießglanz)

Breunig

Lork

Rösler

et al. 2000

Z. anorg. allg. Chem.

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Bis(dimethylstibanyl)oxane (1) and -sulfane (2), the two simplest organoelement species with an Sb±E±Sb fragment (E = O, S), were prepared by alkaline hydrolysis of bromodimethylstibane and by oxidation of tetramethyldistibane with sulfur [18], respectively. As shown by an x-ray structure analysis of compound 1 (m. p. < ±20°C; P2 1 2 1 2 1 , a = 675.9(2), b = 803.1(2), c = 1666.8(4) pm at ±70 ± 2°C; Z = 4; R1 = 0.042), the molecules (O±Sb 198.8 and 209.9 pm, Sb±O±Sb 123.0°) adopt a syn-anti conformation in the solid state and are arranged in zigzag chains along [010] via weak intermolecular O´´Sb interactions (258.5 pm, Sb±O´´Sb 117.8°, O´´Sb±O 173.5°) making use, however, of only one Me 2 Sb moiety. Primary and secondary bond lengths and angles agree very well with corresponding values published for valentinite, the orthorhombic modification of antimony(III) oxide [3]. Bis(dimethylstibanyl)sulfane (2) (m. p. 29 to 31°C) crystallizes in the uncommon space group P6 5 22 (a = 927.8(3), c = 1940.9(7) pm at ±100 ± 2°C; Z = 6; R1 = 0.021). Owing to coordination numbers of (1 + 1) and (2 + 2) for both Me 2 Sb groups and the sulfur atom, respectively, molecules with an approximate syn-syn conformation (S±Sb 249.8 pm, Sb±S±Sb 92.35°) build up a three-dimensional net of double helices which are linked together by Sb´´S contacts (316.4 pm). These parameters shed more light onto the rather complicated structure and bonding situation in stibnite (antimony(III) sulfide [4]). The molecular packing of compound 2 is compared with the structures of relevant inorganic solids, especially with that of b-quartz [37].Gemeinsamkeiten in den Kristallstrukturen der Verbindungen Bis(dimethylstibanyl)oxan und -sulfan und den Mineralien Valentinit und Stibnit (Grauspieûglanz) Inhaltsu È bersicht. Bis(dimethylstibanyl)oxan (1) und -sulfan (2), die beiden einfachsten elementorganischen Vertreter mit einer Sb±E±Sb-Einheit (E = O, S) wurden durch alkalische Hydrolyse von Bromdimethylstiban bzw. durch Oxidation von Tetramethyldistiban mit Schwefel [18] dargestellt. Nach den Ergebnissen einer Ro È ntgenstrukturanalyse an Verbindung 1 (Schmp. < ±20°C; P2 1 2 1 2 1 , a = 675,9(2), b = 803,1(2), c = 1666,8(4) pm bei ±70 ± 2°C; Z = 4; R1 = 0,042) nehmen die Moleku È le (O±Sb 198,8 und 209,9 pm; Sb±O±Sb 123.0°) im Festko È rper die syn-anti Konformation ein und ordnen sich unter Beteiligung nur einer der beiden Me 2 Sb-Gruppen u È ber kurze intermolekulare O´´Sb Kontakte (258,5 pm; Sb±O´´Sb 117,8°; O´´Sb±O 173,5°) zu Zickzack-Ketten la È ngs [010] an. Øhnliche Bindungsla È ngen, -winkel und Kontakte treten in der bekannten Kristallstruktur des Minerals Valentinit, der orthorhombischen Modifikation des Antimon(III)-oxids [3], auf. Bis(dimethylstibanyl)sulfan (2) (Schmp. 29 bis 31°C) kristallisiert in der verha È ltnisma Èûig seltenen Raumgruppe P6 5 22 (a = 927,8(3), c = 1940,9(7) pm bei ±100 ± 2°C; Z = 6; R1 = 0,021). Mit Koordinationszahlen von (1 + 1) fu È r nun alle Me 2 Sb-Gruppen bzw. (2 + 2) fu È r die Schwefelatome bauen die anna È hernd syn-s...

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Reactions of the [Ni6(CO)12]2- dianion with stibine and bismuthine reagents: synthesis and stereophysical characterization of the [Ni10(SbPh)2(CO)18]2- dianion containing a noncentered icosahedral Ni10Sb2 core and Ni2(CO)4(μ2-Ph2SbOSbPh2)2 containing a centrosymmetric eight-membered (NiSbOSb)2 ring

Cited by 41 publications

References 37 publications

Synthesis and Characterization of Hypervalent Organoantimony(III) Compounds Containing the [2‐(Me₂NCH₂)C₆H₄]₂Sb Fragment

Synthesis and Characterization of Hypervalent Organoantimony(III) Compounds Containing the [2‐(Me₂NCH₂)C₆H₄]₂Sb Fragment

Redox and Anion Exchange Chemistry of a Stibine–Nickel Complex: Writing the L, X, Z Ligand Alphabet with a Single Element

Common Features in the Crystal Structures of the Compounds Bis(dimethylstibanyl)oxane and -sulfane, and the Minerals Valentinite and Stibnite (Grauspießglanz)

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Cited by 41 publications

References 37 publications

Synthesis and Characterization of Hypervalent Organoantimony(III) Compounds Containing the [2‐(Me2NCH2)C6H4]2Sb Fragment

Synthesis and Characterization of Hypervalent Organoantimony(III) Compounds Containing the [2‐(Me2NCH2)C6H4]2Sb Fragment

Redox and Anion Exchange Chemistry of a Stibine–Nickel Complex: Writing the L, X, Z Ligand Alphabet with a Single Element

Common Features in the Crystal Structures of the Compounds Bis(dimethylstibanyl)oxane and -sulfane, and the Minerals Valentinite and Stibnite (Grauspießglanz)

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Synthesis and Characterization of Hypervalent Organoantimony(III) Compounds Containing the [2‐(Me₂NCH₂)C₆H₄]₂Sb Fragment

Synthesis and Characterization of Hypervalent Organoantimony(III) Compounds Containing the [2‐(Me₂NCH₂)C₆H₄]₂Sb Fragment