Unknown

Dataset Information

0

Formation of an imidazoliumyl-substituted [(LC)4P4]4+ tetracation and transition metal mediated fragmentation and insertion reaction (LC = NHC).

ABSTRACT: Tetracationic cyclo-tetraphosphane [(LC)4P4]4+ as triflate salt (3[OTf]4) (LC = 4,5-dimethyl-1,3-diisopropyl-imidazol-2-yl) is obtained in high yield from the reduction of [LCPCl2]+ (4[OTf]) with 1,4-bis(trimethylsilyl)-1,4-dihydropyrazine (6) and represents the first salt of the cationic cyclo-phosphane series with the general formula [L n P n ] n+. Theoretical calculations reveal the electrophilic nature of the P atoms within the P4-ring due to the influence of the imidazoliumyl-substituents. Further reduction of 3[OTf]4 with 6 affords the unexpected formation of the notricyclane P7-type cation [(LC)3P7]3+ (9[OTf]3). Selective transition metal mediated [2 + 2]-fragmentation of 3 4+ is achieved when 3[OTf]4 is reacted with Fe2(CO)9, Pd(PPh3)4 and Pt(PPh3)4 leading to the formation of the dicationic diphosphene complexes [(?2-LCP[double bond, length as m-dash]PLC)Fe(CO)4]2+ (12[OTf]2) and [(?2-LCP[double bond, length as m-dash]PLC)M(PPh3)2]2+ (13[OTf]2 for M = Pd; 14[OTf]2 for M = Pt). In contrast, the reaction of 3[OTf]4 with an excess of AuCl(tht) gives rise to the formation of the five-membered ring complex [((LC)4P4)AuCl2]3+ (15[OTf]3), where the Au(i) atom reductively inserts into a P-P bond of 3 4+.

SUBMITTER: Schwedtmann K 

PROVIDER: S-EPMC6640194 | biostudies-literature | 2019 Jul

REPOSITORIES: biostudies-literature

Json Xml
altmetric image

Publications

Formation of an imidazoliumyl-substituted [(L<sub>C</sub>)<sub>4</sub>P<sub>4</sub>]<sup>4+</sup> tetracation and transition metal mediated fragmentation and insertion reaction (L<sub>C</sub> = NHC).

Schwedtmann Kai K   Haberstroh Jan J   Roediger Sven S   Bauzá Antonio A   Frontera Antonio A   Hennersdorf Felix F   Weigand Jan J JJ  

Chemical science 20190530 28

Tetracationic cyclo-tetraphosphane [(L<sub>C</sub>)<sub>4</sub>P<sub>4</sub>]<sup>4+</sup> as triflate salt (<b>3</b>[OTf]<sub>4</sub>) (L<sub>C</sub> = 4,5-dimethyl-1,3-diisopropyl-imidazol-2-yl) is obtained in high yield from the reduction of [L<sub>C</sub>PCl<sub>2</sub>]<sup>+</sup> (<b>4</b>[OTf]) with 1,4-bis(trimethylsilyl)-1,4-dihydropyrazine (<b>6</b>) and represents the first salt of the cationic cyclo-phosphane series with the general formula [L <sub><i>n</i></sub> P <sub><i>n</i></su  ...[more]

Similar Datasets

Unknown Case Study of N-<sup>i</sup> Pr versus N-Mes Substituted NHC Ligands in Nickel Chemistry: The Coordination and Cyclotrimerization of Alkynes at [Ni(NHC)<sub>2</sub> ].
| S-EPMC9299202 | biostudies-literature
Unknown Chemical Bonding in Transition Metal Nitride Os<sub>3</sub>N<sub>3</sub> <sup>+</sup> Cluster: 6π Inorganic Benzene and δ<sup>2</sup>δ*<sup>1</sup>δ*<sup>1</sup> Aromaticity.
| S-EPMC6643571 | biostudies-literature
Unknown Acceleration of CO<sub>2</sub> insertion into metal hydrides: ligand, Lewis acid, and solvent effects on reaction kinetics.
| S-EPMC6115618 | biostudies-literature
Unknown Proximity-induced magnetism in transition-metal substituted graphene.
| S-EPMC4522683 | biostudies-literature
Unknown Transition Metal-Promoted V<sub>2</sub>CO<sub>2</sub> (MXenes): A New and Highly Active Catalyst for Hydrogen Evolution Reaction.
| S-EPMC5102657 | biostudies-literature
Unknown Corona Discharge and Field Electron Emission in Ambient Air Using a Sharp Metal Needle: Formation and Reactivity of CO<sub>3</sub> <sup>-•</sup> and O<sub>2</sub> <sup>-•</sup>.
| S-EPMC8697365 | biostudies-literature
Unknown Transition-metal-free synthesis of 3-sulfenylated chromones via KIO<sub>3</sub>-catalyzed radical C(sp<sup>2</sup>)-H sulfenylation.
| S-EPMC5629394 | biostudies-literature
Unknown From the Free Ligand to the Transition Metal Complex: FeEDTA<sup>-</sup> Formation Seen at Ligand K-Edges.
| S-EPMC9277664 | biostudies-literature
Unknown Effect of Alkali and Trivalent Metal Ions on the High-Pressure Phase Transition of [C<sub>2</sub>H<sub>5</sub>NH<sub>3</sub>]M<sup>I</sup> <sub>0.5</sub>M<sup>III</sup> <sub>0.5</sub>(HCOO)<sub>3</sub> (M<sup>I</sup> = Na, K and M<sup>III</sup> = Cr, Al) Heterometallic Perovskites.
| S-EPMC7497711 | biostudies-literature
Unknown Stabilization of Linear C<sub>3</sub> by Two Donor Ligands: A Theoretical Study of L-C<sub>3</sub> -L (L=PPh<sub>3</sub> , NHC<sup>Me</sup> , cAAC<sup>Me</sup> )*.
| S-EPMC7702110 | biostudies-literature