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The reactions of the triruthenium cluster complex [Ru3(mu-H)(mu3-eta2-HNNMe2)(CO)9] (1; H2NNMe2=1,1-dimethylhydrazine) with alkynes (PhC triple bond CPh, HC triple bond CH, MeO2CC triple bond CCO2Me, PhC triple bond CH, MeO2CC triple bond CH, HOMe2CC triple bond CH, 2-pyC triple bond CH) give trinuclear complexes containing edge-bridging and/or face-capping alkenyl ligands. Whereas the edge-bridged products are closed triangular species (three Ru-Ru bonds), the face-capped products are open derivatives (two Ru-Ru bonds). For terminal alkynes, products containing gem (RCCH2) and/or trans (RHCCH) alkenyl ligands have been identified in both edge-bridging and face-capping positions, except for the complex [Ru3(mu3-eta2-HNNMe2)(mu3-eta3-HCCH-2-py)(mu-CO)(CO)7], which has the two alkenyl H atoms in a cis arrangement. Under comparable reaction conditions (1:1 molar ratio, THF at reflux, time required for the consumption of complex 1), some reactions give a single product, but most give mixtures of isomers (not all the possible ones), which were separated. To determine the effect of the hydrazido ligand, the reactions of [Ru3(mu-H)(mu3-eta2-MeNNHMe)(CO)9] (2; HMeNNHMe=1,2-dimethylhydrazine) with PhC triple bond CPh, PhC triple bond CH, and HC triple bond CH were also studied. For edge-bridged alkenyl complexes, the Ru--Ru edge that is spanned by the alkenyl ligand depends on the position of the methyl groups on the hydrazido ligand. For face-capped alkenyl complexes, the relative orientation of the hydrazido and alkenyl ligands also depends on the position of the methyl groups on the hydrazido ligand. A kinetic analysis of the reaction of 1 with PhC[triple chemical bond]CPh revealed that the reaction follows an associative mechanism, which implies that incorporation of the alkyne in the cluster is rate-limiting and precedes the release of a CO ligand. X-ray diffraction, IR and NMR spectroscopy, and calculations of minimum-energy structures by DFT methods were used to characterize the products. A comparison of the absolute energies of isomeric compounds (obtained by DFT calculations) helped rationalize the experimental results.

have been determined by X-ray diffraction.[Au{MCl(HMDS) 2 }(THT)]

An efficient synthesis of 2-di-tert-butylphosphanylmethylpyrrole( HpyrmPtBu 2 ), by treating 2-dimethylaminomethylpyrrole( HpyrmNMe 2 )w ith tBu 2 PH at 135 8Ci nt he absence of any solvent,h as allowed the preparation of the new PGeP germyleneG e(pyrmPtBu 2 ) 2 (1), by treating [GeCl 2 (dioxane)] with LipyrmPtBu 2 ,i nw hich the Ge atom is stabilized by intramolecular interactions with one (solid state) or both (solution) of its phosphane groups.R eactions of germylene 1 with Group 10 metald ichlorido complexes containing easily displaceablel igandsh ave led to [MCl{k 3 P,Ge,P-GeCl(pyrmPtBu 2 ) 2 }] [M = Ni (2), Pd (3), Pt (4)], which have an unflawed square-planar metale nvironment.Treatmento fg ermylene 1 with [AuCl(tht)] (tht = tetrahydrothiophene) rendered[ Au{k 3 P,Ge,P-GeCl(pyrmPtBu 2 ) 2 }] (5), which is ar are case of aT -shaped gold(I) complex. The hydrolysis of 5 gave the linear gold(I) derivative [Au(kP-HpyrmPtBu 2 ) 2 ]Cl (6). Complexes 2-5 contain aP GeP pincer chloridogermyl ligandt hat arises from the insertionof the Ge atom of germylene 1 into aM ÀCl bond of the corresponding metal reagent. The bondingi nt hese molecules has been studied by DFT/NBO/QTAIM calculations. These results demonstrate that the great flexibility of germylene 1 makesi tabetter precursor to PGeP pincer complexes than the previouslyk nown germylenes of this type.[a] Prof.Supporting information (containingt he experimental details and analytical, spectroscopic, structural(XRD), and theoretical (DFT,QTAIM) and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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