2020
DOI: 10.1002/ejic.202000747
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Size Matters: Synthesis of Group 13 Metal‐Substituted Dipnictanes by E‐C Bond Homolysis

Abstract: Pnictanes Cp*(Ph)ECl (E = As 1, Sb 2; Cp* = C5Me5) react with group 13 diyls LM (M = Al, Ga, In; L = HC[C(Me)N(Dip)]2, Dip = 2,6‐iPr2C6H3) with oxidative addition of the E‐Cl bond to a unique series of metalylpnictanes [L(Cl)M](Ph)ECp* (E = As, M = Al 3, Ga 4, In 5; E = Sb, M = Al 6, Ga 7, In 8). Thermal treatment of 4 and 6–8 results in homolytic E‐C bond scission with Cp* radical liberation, yielding the corresponding dipnictanes {[L(Cl)M](Ph)E}2 (E = As, M = Ga 9; E = Sb, M = Al 10, Ga 11, In 12). Compounds… Show more

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Cited by 24 publications
(23 citation statements)
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References 75 publications
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“…The 1 HNMR spectrum of compound 1 exhibits two sets of resonances for the Dipp groups of the b-diketiminate ligand as was previously observed for LGa-substituted gallapnictenes, [4] dipnictanes, [13] dipnictenes, [14] radicals, [15] and other complexes, [16] whereas that of compound 2 shows one set of signals for the b-diketiminate ligand, indicating ad ynamic chloride ion shifting between two Ga atoms in solution. This was proven by variable-temperature (VT) 1 HNMR studies ( Figure S34).…”
Section: Resultssupporting
confidence: 69%
See 1 more Smart Citation
“…The 1 HNMR spectrum of compound 1 exhibits two sets of resonances for the Dipp groups of the b-diketiminate ligand as was previously observed for LGa-substituted gallapnictenes, [4] dipnictanes, [13] dipnictenes, [14] radicals, [15] and other complexes, [16] whereas that of compound 2 shows one set of signals for the b-diketiminate ligand, indicating ad ynamic chloride ion shifting between two Ga atoms in solution. This was proven by variable-temperature (VT) 1 HNMR studies ( Figure S34).…”
Section: Resultssupporting
confidence: 69%
“…[21b] The 1 H,13 C, and31 PNMR spectra of compound 4 dissolved in [D 8 ]toluene and two drops of THF show largely shifted signals due to THF coordination, whereas the 19 FNMR spectrum is virtually identical with that in [D 8 ]toluene (…”
mentioning
confidence: 99%
“…Die Verbindungen 1 und 2 sind löslich in organischen Lösungsmitteln und für Monate unter Schutzgasatmosphäre bei Raumtemperatur lagerfähig. Das 1 H‐NMR‐Spektrum von Verbindung 1 zeigt zwei Signalsätze für die Dipp‐Gruppen des β‐Diketiminatliganden, was bereits für Ga‐substituierte Gallapniktene, [4] Dipniktane, [13] Dipniktene, [14] Radikale [15] und andere Komplexe [16] beobachtet wurde, während das 1 H‐NMR‐Spektrum von Verbindung 2 einen Signalsatz des β‐Diketiminatliganden aufweist. Dies deutet auf einen dynamischen Chloridionenaustausch in Lösung zwischen den Ga‐Atomen hin, was durch temperaturabhängige 1 H‐NMR‐Studien (Abbildung S34) verifiziert wurde.…”
Section: Ergebnisse Und Diskussionunclassified
“…Das IR-Spektrum von Verbindung 3 beinhaltet eine C-O-Streckschwingungsbande bei 1739 cm À1 ,die mit der von Na(OCP)•-(Dioxan) 2.5 (1755 cm À1 ) [21a] übereinstimmt, aber kleiner als die des "freien" OCP-Anions (1791 cm À1 ) [21b] ist, was die vermutete OCP-Koordination unterstützt. Die 1 H-, 13 C-und 31 P-NMR-Spektren einer Lçsung von Verbindung 4 in Toluol-d 8 , die mit zwei Tr opfen THF versetzt wurde,z eigen eine deutliche Verschiebung der Signale infolge der THF-Koordination, während das 19 F-NMR-Spektrum nahezu identisch zu dem in reinem Toluol-d 8 ist (Abbildungen S35-S38). Dies bestätigt den elektrophilen Charakter des Kations in 4, welcher sich in der Reaktion mit 4-Dimethylaminopyridin (DMAP;Abbildungen S39-S42) bestätigte.…”
unclassified
“…[8][9][10][11][12][13][14][15] In this work, we devote our attention to the reactivity of the neutral six-membered NHC analogues featuring a group 13 element (G13-6-Rea). Although the understanding of the six-membered-ring G13-6-Rea molecules has certainly grown in recent years, [41][42][43][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59][60] our knowledge concerning their relative chemical reactivity remains primitive compared to that of ve-membered-ring NHC analogues bearing a central group 14 element. [22][23][24][25] In this study, we thus chose two typical chemical reactions (insertion, eqn (1), and cycloaddition, eqn (2)) based on density functional theory (DFT) to investigate the origin of the activation barriers for group 13 analogs of the six-membered NHCs.…”
Section: Introductionmentioning
confidence: 99%