Reactivity Studies of
(Phenylethynyl)germylene LGeCCPh
(L = HC[C(Me)N-2,6‑<i>i</i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>]<sub>2</sub>) toward Pentafluorophenylcopper(I), -silver(I),
and -gold(I) Complexes
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Abstract
Reactions of (phenylethynyl)germylene LGeCCPh
(L = HC[C(Me)N-2,6-<i>i</i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>]<sub>2</sub>)
with 0.25 equiv of (CuC<sub>6</sub>F<sub>5</sub>)<sub>4</sub>, 1 equiv
of AgC<sub>6</sub>F<sub>5</sub>·MeCN, and 1 equiv of AuC<sub>6</sub>F<sub>5</sub>·SC<sub>4</sub>H<sub>8</sub>, respectively,
yielded LGe(CCPh)CuC<sub>6</sub>F<sub>5</sub> (<b>1</b>), [(LGeCCPh)<sub>2</sub>Ag]<sup>+</sup>[Ag(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>]<sup>−</sup> (<b>2</b>),
and LGe(CCPh)AuC<sub>6</sub>F<sub>5</sub> (<b>3</b>).
Complexes <b>1</b>–<b>3</b> were characterized
by IR and NMR spectroscopy and X-ray crystallography. Compound <b>1</b> shows a bonding pattern of the CuC<sub>6</sub>F<sub>5</sub> entity by both the phenylethynyl CC linkage and the L ligand
backbone of the γ-C atom, while <b>3</b> exhibits a bonding
mode of the AuC<sub>6</sub>F<sub>5</sub> entity at the germylene center.
Compound <b>2</b> is an ionic derivative featuring the Ge–Ag
donor–acceptor bond formed under redistribution of the AgC<sub>6</sub>F<sub>5</sub> entity. Further reactions of <b>1</b> with
(CuC<sub>6</sub>F<sub>5</sub>)<sub>4</sub>, AgC<sub>6</sub>F<sub>5</sub>·MeCN, and AuC<sub>6</sub>F<sub>5</sub>·SC<sub>4</sub>H<sub>8</sub> afforded the complexes LGe(CCPh)(CuC<sub>6</sub>F<sub>5</sub>)(MC<sub>6</sub>F<sub>5</sub>) (M = Cu (<b>4</b>), Ag
(<b>5</b>), Au (<b>6</b>)). Compounds <b>4</b>–<b>6</b> were characterized by IR and NMR spectroscopy, and <b>5</b> and <b>6</b> were further investigated by X-ray crystallography.
Compounds <b>4</b>–<b>6</b> all show an additional
bonding of the respective MC<sub>6</sub>F<sub>5</sub> moiety at the
germylene center of <b>1</b>. These studies reveal a multiple
donor reactivity of LGeCCPh. The slightly different Lewis
acidic properties of the congeneric pentafluorophenylcopper(I), -silver(I),
and -gold(I) complexes as acceptors are thus disclosed
