Benzotriazole

Santandrea, Jeffrey; Collins, Shawn K.

doi:10.1002/047084289x.rn01871

Cited by 1 publication

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“…The Zintl phase precursor K 3 P 7 was synthesized according to a previously reported synthetic procedure from a mixture of the elements (K: 99.95%, Strem; P: 99.99%, Aldrich). 39 Bis(2,6diisopropylphenyl)carbodiimide was synthesized according to the method reported by Cowley and co-workers. 40 Brookhart's acid, [H(OEt 2 ) 2 ][BAr F 4 ], was prepared according to a modified procedure reported by Brookhart et al and stored in a glovebox freezer at −25 °C.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Hydrophosphination of Carbodiimides Using Protic Heptaphosphide Cages: A Unique Effect of the Bimodal Activity of Protonated Group 15 Zintl Ions

Turbervill

Goicoechea

2012

Organometallics

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Direct reaction of the hydrogen heptaphosphide dianion, [HP 7 ] 2− (1), with carbodiimides RNCNR (R = Dipp (2,6diisopropylphenyl), i Pr, Cy) afforded the amidine-functionalized Zintl ions [P 7 C(NHR)(NR)] 2− (R = Dipp (2), i Pr (3), and Cy (4)). The bimodal activity of 1, which contains both negatively charged phosphide vertices alongside "electron-precise" phosphine-like nuclei allows for the direct hydrophosphination of the carbodiimides without need for an external proton source. Further reaction of the bis(2,6diisopropylphenyl)amidine-functionalized cluster 2 with a proton source such as4 ] affords the protonated monoanionic species [HP 7 C(NHDipp)(NDipp)] − (5). As with 1, species 5 also has bimodal character, and additional hydrophosphination reactions are possible by reacting 5 with RNCNR to yield the bisfunctionalized monoanions { 6), i Pr (7), and Cy ( 8)). All species were characterized by multielement NMR spectroscopy and electrospray mass spectrometry. In addition clusters 3, 5, and 6−8 were characterized by single-crystal X-ray diffraction in [K(18-crown-6)•hex, and [K(2,2,2-crypt)][8]•0.65THF•0.35hex, respectively. Density functional theory level calculations were conducted on all anionic species to probe their electronic structure.

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Section: ■ Experimental Sectionmentioning

confidence: 99%