Publication | Open Access
Copper Clusters Containing Hydrides in Trigonal Pyramidal Geometry
49
Citations
52
References
2020
Year
Structurally precise copper hydrides [Cu<sub>11</sub>H<sub>2</sub>{S<sub>2</sub>P(O<sup><i>i</i></sup>Pr)<sub>2</sub>}<sub>6</sub>(C≡CR)<sub>3</sub>], R = Ph (<b>1</b>), C<sub>6</sub>H<sub>4</sub>F (<b>2</b>), and C<sub>6</sub>H<sub>4</sub>OMe (<b>3</b>), were first synthesized from the polyhydrido copper cluster [Cu<sub>20</sub>H<sub>11</sub>{S<sub>2</sub>P(O<sup><i>i</i></sup>Pr)<sub>2</sub>}<sub>9</sub>] with nine equivalents of terminal alkynes. Later, their isolated yields were significantly improved by direct synthesis from [Cu(CH<sub>3</sub>CN)<sub>4</sub>](PF<sub>6</sub>), [NH<sub>4</sub>][S<sub>2</sub>P(O<sup><i>i</i></sup>Pr)<sub>2</sub>], NaBH<sub>4</sub>, and alkynes along with NEt<sub>3</sub> in THF. <b>1</b>, <b>2</b>, and <b>3</b> were fully characterized by single-crystal X-ray diffraction, ESI-MS, and multinuclear NMR spectroscopy. All three clustershave 11 copper atoms, adopting 3,3,4,4,4-pentacapped trigonal prismatic geometry, with two hydrides inside the Cu<sub>11</sub> cage, the position of which was ascertained by a single-crystal neutron diffraction structure of cluster <b>1</b> co-crystallized with a [Cu<sub>7</sub>(H){S<sub>2</sub>P(O<sup><i>i</i></sup>Pr)<sub>2</sub>}<sub>6</sub>] (<b>4</b>) cluster. Six dithiophosphate and three alkynyl ligands stabilize the Cu<sub>11</sub>H<sub>2</sub> core in which the two hydrides adopt a trigonal pyramidal coordination mode. This coordination mode is so far unprecedented for hydride. The <sup>1</sup>H NMR resonance frequency of the two hydrides appears at 4.8 ppm, a value further confirmed by <sup>2</sup>H NMR spectroscopy for their deuteride derivatives [Cu<sub>11</sub>(D)<sub>2</sub>{S<sub>2</sub>P(O<sup><i>i</i></sup>Pr)<sub>2</sub>}<sub>6</sub>(C≡CR)<sub>3</sub>]. A DFT investigation allows understanding the bonding within this new type of copper(I) hydrides.
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