Synthesis, structure, and reaction of tricoordinate stibine and tetracoordinate stiboranide

Jiang, Xin‐Dong; Yamamoto, Yohsuke

doi:10.1016/j.jorganchem.2009.12.009

Cited by 11 publications

(11 citation statements)

References 44 publications

(55 reference statements)

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“…Previous work with hexafluoro-α-cumyl alkoxide was undertaken to stabilize trigonal-bipyramidal geometries, and complexes with the same dianionic, four-membered chelate ring as in 5 were structurally characterized with M = Ge(IV), Sb(III), , Bi(III). , Hexafluoro-α-cumyl alcohol was doubly deprotonated by directed dilithiation and added to the p-block halides. , The M–C bond distances are generally longer than those of 5 , namely 2.133 and 2.162 Å in [NEt 4 ][Sb(OC(C 6 H 4 )(CF 3 ) 2 ) 2 ] and 2.249 and 2.237 Å in [NEt 4 ][Bi(OC(C 6 H 4 )(CF 3 ) 2 ) 2 ]. , The only structure with M–C bonds similar to those of 5 is [Ge(OC(C 6 H 4 )(CF 3 ) 2 ) 2 ], with Ge–C distances of 1.896 and 1.900 Å. In other p-block structures with this geometry, lone pairs on the central atoms usually promote a trigonal-bipyramidal structure, rather than square pyramidal.…”

Section: Resultsmentioning

confidence: 99%

“…The Cu(I) trimer was compared to a 1:1 electrolyte, tetra-n-butyl ammonium hexafluorophosphate (TBAPF 6 ), and the previously reported 2:1 electrolyte {K(18C6)} 2 [Cu(OC 6 F 5 ) 4 ] 33 (Figure 4). Compound Previous work with hexafluoro-α-cumyl alkoxide was undertaken to stabilize trigonal-bipyramidal geometries, 34 and complexes with the same dianionic, four-membered chelate ring as in 5 were structurally characterized 35 with M = Ge(IV), 36 Sb(III), 37,38 Bi(III). 39,40 Hexafluoro-α-cumyl alcohol was doubly deprotonated by directed dilithiation and added to the p-block halides.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Room Temperature Stable Organocuprate Copper(III) Complex

et al. 2013

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The paramagnetic trigonal-planar copper complexes {K(18C6)}-[Cu II (OC(CH 3 )(CF 3 ) 2 ) 3 ] (2) and K[Cu II (OC(C 6 H 5 )(CF 3 ) 2 ) 3 ] (3) have been prepared and characterized, including X-ray crystallography, in 61% and 3% yields, respectively. The latter complex does not form preferentially, because CuBr 2 and KOC(C 6 H 5 )(CF 3 ) 2 ) 3 also form the diamagnetic complexes {K(18C6)}-[K 2 {Cu I (OC(C 6 H 5 )(CF 3 ) 2 ) 2 } 3 ] (4) and {K(18C6)}[Cu III (OC(C 6 H 4 )(CF 3 ) 2 ) 2 ] (5). These species were characterized by X-ray crystallography, UV−vis spectroscopy, 1 H, 13 C{ 1 H}, and 19 F{ 1 H} NMR spectroscopy, and elemental analysis. The unique organocuprate Cu(III) species with {O 2 C 2 } coordination was formed by ortho metalation of two phenyl rings, resulting in trans-{O 2 C 2 } coordination of Cu(III), and is stable at room temperature in the solid state and in dark solutions of THF.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Room Temperature Stable Organocuprate Copper(III) Complex

et al. 2013

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“…Recently, organoantimony oxide was synthesized and found to be recoverable reagent efficient for CO 2 chemical fixation [28]. Ionic organoantimony complexes also have been developed [29][30][31]. However, the use of organoantimony compounds as catalysts in organic synthesis is rarely reported [25,26].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and structure of an air-stable organoantimony complex and its use as a catalyst for direct diastereoselective Mannich reactions in water

Xia

Qiu

Yin

et al. 2010

Journal of Organometallic Chemistry

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“…The arsoranides 4 were easily separated from 2 by recrystallization (n-hexane) or TLC (n-hexane/CH 2 Cl 2 ). 67 Compound 4a-Li bearing the Martin ligand (A) was very stable to water or air, 75 but 4b−Na and 4c−Na showed instability and slowly gave 3b and 3c, respectively.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis and Characterization of Antiapicophilic Arsoranes and Related Compounds

et al. 2012

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Utilizing bulky bidentate ligand systems with C(2)F(5) and n-C(3)F(7) groups, antiapicophilic arsoranes (5b and 5c, respectively) were synthesized. A kinetic study on the isomerization of these arsoranes to their more stable isomers showed that the barriers increased in the order of CF(3) < C(2)F(5) < n-C(3)F(7) in accord with their steric bulk. It was also revealed that the degree of freezing isomerization was larger for the change from CF(3) to C(2)F(5) than from C(2)F(5) to n-C(3)F(7), obvious from the differences in activation free energy at 363 K of 1.6 and 0.3 kcal mol(-1), respectively. X-ray structural analysis of several precursors of these two systems disclosed the unique structures of these compounds.

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Synthesis, structure, and reaction of tricoordinate stibine and tetracoordinate stiboranide

Cited by 11 publications

References 44 publications

Room Temperature Stable Organocuprate Copper(III) Complex

Room Temperature Stable Organocuprate Copper(III) Complex

Synthesis and structure of an air-stable organoantimony complex and its use as a catalyst for direct diastereoselective Mannich reactions in water

Synthesis and Characterization of Antiapicophilic Arsoranes and Related Compounds

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