1‐Cyclohepta‐2,4,6‐trienyl‐selanes—a77Se NMR study: Indirect nuclear77Se13C spin–spin coupling constants and application of density functional theory (DFT) calculations

Wrackmeyer, Bernd; Hernández, Zureima García; Herberhold, Max

doi:10.1002/mrc.1946

Cited by 23 publications

(7 citation statements)

References 65 publications

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“…Numerous investigations of calculated selenium magnetic shielding and/or chemical shift tensors have been reported [72][73][74][75][76][77][78][79][80]. Additionally, recent theoretical computations of indirect spin-spin coupling constants involving selenium have appeared in the literature [81][82][83]. The interested reader is encouraged to pursue these references for a more detailed description of the intricacies of calculating 77 Se NMR parameters.…”

Section: Structurementioning

confidence: 99%

Solid-state selenium-77 NMR

Demko

Wasylishen

2009

Progress in Nuclear Magnetic Resonance Spectroscopy

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Section: Structurementioning

confidence: 99%

Solid-state selenium-77 NMR

Demko

Wasylishen

2009

Progress in Nuclear Magnetic Resonance Spectroscopy

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“…Our current interest in tropylium derivatives [18][19][20] prompted us to study the reaction of 19 with tropylium bromide, C 7 H 7 Br. Surprisingly, the reaction went towards the bis(diselane) 18, and the tropylium derivative could not be observed.…”

Section: Methodsmentioning

confidence: 99%

“…In the case of other trimethylsilylselanes Me 3 Si-SeR, this type of reaction gave tropylium selenides C 7 H 7 -Se-R, most of which are fairly stable until room temperature before they decompose. 20 Another attempt was made to extend the silane chemistry of 3, aiming at the synthesis of a spirosilane by treatment of SiCl 4 with two equivalents of 3. Instead of the desired silane, again the bis(diselane) 18 could be obtained and could be isolated in reasonably high yield.…”

Section: Methodsmentioning

confidence: 99%

Novel main group chemistry of the 1,2-diselenido-1,2-dicarba-closo-dodecaborane(12) dianion

Hernández¹,

Wrackmeyer²,

Kempe³

et al. 2007

Arkivoc

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Recent results are summarized on some new aspects of the main group chemistry of the 1,2-diselenido-1,2-dicarba-closo-dodecaborane(12) dianion 3, [1,2-(1,2-C 2 B 10 H 10 )Se 2 ] 2-. The reactions of 3 with organoelement-Group 14 dichlorides (Ph 2 CCl 2 , Me 2 SiCl 2 , Ph 2 SiCl 2 , Me 2 SnCl 2 , Ph 2 SnCl 2 ) and phenylphosphorus dichloride (PhPCl 2 ) afforded novel five-member heterocycles along with other products. In the case of Ph 2 SiCl 2 , the expected product 6 was accompanied by another five-member ring 8 containing the Ph 2 Si-Se-Se moiety. The phospholane 13 could be oxidised to the sulfide 14 and the selenide 15, and partial hydrolysis gave the selenophosphonic acid 16 along with the bis(diselane) 18 and decomposition. The dianion 3 was converted by oxidative coupling into the bis(diselane) 18, an eight-member ring with annellated carborane moieties. Symmetric cleavage of this ring in 18 took place by oxidative addition of 18 to bis(triphenylphosphane)ethene-platinum(0) to give the (Ph 3 P) 2 Pt(II) complex 20 with the chelating 1,2-diselenido-1,2-dicarba-closo-dodecaborane(12) ligand. Oxidative addition of the five-member heterocycles containing Se-Sn-Se fragments (9, 11) to bis(triphenylphosphane)ethene-platinum(0) proceeded at low temperature by insertion of the (PPh 3 ) 2 Pt fragment into one of the Sn-Se bonds (21, 22). The reaction of 11 with bis(triphenylphosphane)ethene-platinum(0) took place by oxidative addition of the P-Se bond, followed by rearrangement (25). The molecular structures of the five-member rings with annellated carborane units 4 (CPh 2 ), 11 (SnPh 2 ), 13 (PPh), 14 (PhP=S), 20 (Pt(PPh 3 ) 2 , and of the bis(diselane) 18 were determined by X-ray analyses.The proposed solution-state structures of the new compounds followed from consistent sets of multinuclear magnetic resonance data (

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“…It should also be noted that magnitude and trend of experimental data (Table 1). [40] Figure 7A) independent of the structure. Therefore, dynamic processes that involve the five-membered ring in solution cannot be ruled out.…”

mentioning

confidence: 86%

Synthesis and Reactivity of 4,5‐[1,2‐Dicarba‐closo‐dodecaborano(12)]‐1,3‐diselenacyclopentane: Opening of the Icosahedron to Give a Zwitterionic Intermediate and Conversion into 7,8‐Dicarba‐nido‐undecaborate(1−)

Wrackmeyer

Klimkina

Milius

et al. 2011

Chemistry A European J

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The reaction of the 1,2-diselenolato-1,2-dicarba-closo-dodecaborane(12) dianion [1,2-(1,2-C(2)B(10)H(10))Se(2)](2-) with dichloromethane (CH(2)Cl(2) or CD(2)Cl(2)) in the presence of donor solvents gave 4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3-diselenacyclopentane, the title compound, which was characterized by X-ray structural analysis and NMR spectroscopy ((1)H, (11)B, (13)C, and (77)Se). In the presence of pyridine, opening of the icosahedron took place, and a zwitterionic intermediate was isolated and fully characterized in the solid state by X-ray diffraction and in solution by multinuclear magnetic resonance techniques. Although such types of intermediates, prior to deboronation of the ortho-carborane cage, have been proposed several times, this is first example for which the structure has been confirmed unambiguously. This intermediate possesses a nido structure and contains a 7,8-dicarba-nido-undecaborate(1-) anion and a boronium cation, the latter with two pyridine rings linked to the boron atom, which has been extruded from the cage. It was shown that this process is reversible as long as the deboronation is not complete. The formation of the intermediate is accompanied by deboronation, which leads to the 7,8-dicarba-nido-undecaborate(1-) anion. The latter was prepared independently by conventional routes from the title compound, isolated as crystalline material as the tetrabutyl ammonium salt, and characterized by X-ray structural analysis and multinuclear magnetic resonance spectroscopy ((1)H, (11)B, (13)C, and (77)Se).

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1‐Cyclohepta‐2,4,6‐trienyl‐selanes—a⁷⁷Se NMR study: Indirect nuclear⁷⁷Se¹³C spin–spin coupling constants and application of density functional theory (DFT) calculations

Cited by 23 publications

References 65 publications

Solid-state selenium-77 NMR

Solid-state selenium-77 NMR

Novel main group chemistry of the 1,2-diselenido-1,2-dicarba-closo-dodecaborane(12) dianion

Synthesis and Reactivity of 4,5‐[1,2‐Dicarba‐closo‐dodecaborano(12)]‐1,3‐diselenacyclopentane: Opening of the Icosahedron to Give a Zwitterionic Intermediate and Conversion into 7,8‐Dicarba‐nido‐undecaborate(1−)

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