{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"omics_type":["Unknown"],"volume":["8(9)"],"submitter":["Filippou AC"],"funding":["Jürgen Manchot Stiftung","Rheinische Friedrich-Wilhelms-Universität Bonn"],"pubmed_abstract":["A systematic, efficient approach to first complexes containing a triple bond between niobium and the elements silicon, germanium or tin is reported. The approach involves a metathetical exchange of the niobium-centered nucleophile (NMe<sub>4</sub>)[Nb(CO)<sub>4</sub>(κ<sup>2</sup>-tmps)] (<b>1</b>) (tmps = MeSi(CH<sub>2</sub>PMe<sub>2</sub>)<sub>3</sub>) with a suitable organotetrel(ii)halide. Compound <b>1</b> was obtained from (NMe<sub>4</sub>)[Nb(CO)<sub>6</sub>] and the triphosphane tmps by photodecarbonylation. Reaction of <b>1</b> with the disilene <i>E</i>-Tbb(Br)Si[double bond, length as m-dash]Si(Br)Tbb in the presence of 4-dimethylaminopyridine afforded selectively the red-brown silylidyne complex [(κ<sup>3</sup>-tmps)(CO)<sub>2</sub>Nb[triple bond, length as m-dash]Si-Tbb] (<b>2-Si</b>, Tbb = 4-<i>tert</i>-butyl-2,6-bis(bis(trimethylsilyl)methyl)phenyl). Similarly, treatment of <b>1</b> with E(Ar<sup>Mes</sup>)Cl (E = Ge, Sn; Ar<sup>Mes</sup> = 2,6-mesitylphenyl) afforded after elimination of (NMe<sub>4</sub>)Cl and two CO ligands the deep magenta colored germylidyne complex [(κ<sup>3</sup>-tmps)(CO)<sub>2</sub>Nb[triple bond, length as m-dash]Ge-Ar<sup>Mes</sup>] (<b>3-Ge</b>), and the deep violet, light-sensitive stannylidyne complex [(κ<sup>3</sup>-tmps)(CO)<sub>2</sub>Nb[triple bond, length as m-dash]Sn-Ar<sup>Mes</sup>] (<b>3-Sn</b>), respectively. Formation of <b>3-Sn</b> proceeds <i>via</i> the niobiastannylene [(κ<sup>3</sup>-tmps)(CO)<sub>3</sub>Nb-SnAr<sup>Mes</sup>] (<b>4-Sn</b>), which was detected by IR and NMR spectroscopy. The niobium tetrylidyne complexes <b>2-Si</b>, <b>3-Ge</b> and <b>3-Sn</b> were fully characterized and their solid-state structures determined by single-crystal X-ray diffraction studies. All complexes feature an almost linear tetrel coordination and the shortest Nb-E bond lengths (<i>d</i>(Nb-Si) = 232.7(2) pm; <i>d</i>(Nb-Ge) = 235.79(4) pm; <i>d</i>(Nb-Sn) = 253.3(1) pm) reported to date. Reaction of <b>3-Ge</b> with a large excess of H<sub>2</sub>O afforded upon cleavage of the Nb-Ge triple bond the hydridogermanediol Ge(Ar<sup>Mes</sup>)H(OH)<sub>2</sub>. Photodecarbonylation of [CpNb(CO)<sub>4</sub>] (Cp = η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>) in the presence of Ge(Ar<sup>Mes</sup>)Cl afforded the red-orange chlorogermylidene complex [Cp(CO)<sub>3</sub>Nb[double bond, length as m-dash]Ge(Ar<sup>Mes</sup>)Cl] (<b>5-Ge</b>). The molecular structure of <b>5-Ge</b> features an upright conformation of the germylidene ligand, a trigonal-planar coordinated Ge atom, and a Nb-Ge double bond length of 251.78(6) pm, which lies in-between the Nb-Ge triple bond length of <b>3-Ge</b> (235.79(4) pm) and a Nb-Ge single bond length (267.3 pm). Cyclic voltammetric studies of <b>2-Si</b>, <b>3-Ge</b>, and <b>3-Sn</b> reveal several electron-transfer steps. One-electron oxidation and reduction of the germylidyne complex of <b>3-Ge</b> in THF are electrochemically reversible suggesting that both the radical cation and radical anion of <b>3-Ge</b> are accessible species in solution."],"journal":["Chemical science"],"pagination":["6290-6299"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC5956830"],"repository":["biostudies-literature"],"pubmed_title":["Triple bonds of niobium with silicon, germaniun and tin: the tetrylidyne complexes [(κ<sup>3</sup>-tmps)(CO)<sub>2</sub>Nb[triple bond, length as m-dash]E-R] (E = Si, Ge, Sn; tmps = MeSi(CH<sub>2</sub>PMe<sub>2</sub>)<sub>3</sub>; R = aryl)."],"pmcid":["PMC5956830"],"pubmed_authors":["Filippou AC","Hoffmann D","Schnakenburg G"],"additional_accession":[]},"is_claimable":false,"name":"Triple bonds of niobium with silicon, germaniun and tin: the tetrylidyne complexes [(κ<sup>3</sup>-tmps)(CO)<sub>2</sub>Nb[triple bond, length as m-dash]E-R] (E = Si, Ge, Sn; tmps = MeSi(CH<sub>2</sub>PMe<sub>2</sub>)<sub>3</sub>; R = aryl).","description":"A systematic, efficient approach to first complexes containing a triple bond between niobium and the elements silicon, germanium or tin is reported. The approach involves a metathetical exchange of the niobium-centered nucleophile (NMe<sub>4</sub>)[Nb(CO)<sub>4</sub>(κ<sup>2</sup>-tmps)] (<b>1</b>) (tmps = MeSi(CH<sub>2</sub>PMe<sub>2</sub>)<sub>3</sub>) with a suitable organotetrel(ii)halide. Compound <b>1</b> was obtained from (NMe<sub>4</sub>)[Nb(CO)<sub>6</sub>] and the triphosphane tmps by photodecarbonylation. Reaction of <b>1</b> with the disilene <i>E</i>-Tbb(Br)Si[double bond, length as m-dash]Si(Br)Tbb in the presence of 4-dimethylaminopyridine afforded selectively the red-brown silylidyne complex [(κ<sup>3</sup>-tmps)(CO)<sub>2</sub>Nb[triple bond, length as m-dash]Si-Tbb] (<b>2-Si</b>, Tbb = 4-<i>tert</i>-butyl-2,6-bis(bis(trimethylsilyl)methyl)phenyl). Similarly, treatment of <b>1</b> with E(Ar<sup>Mes</sup>)Cl (E = Ge, Sn; Ar<sup>Mes</sup> = 2,6-mesitylphenyl) afforded after elimination of (NMe<sub>4</sub>)Cl and two CO ligands the deep magenta colored germylidyne complex [(κ<sup>3</sup>-tmps)(CO)<sub>2</sub>Nb[triple bond, length as m-dash]Ge-Ar<sup>Mes</sup>] (<b>3-Ge</b>), and the deep violet, light-sensitive stannylidyne complex [(κ<sup>3</sup>-tmps)(CO)<sub>2</sub>Nb[triple bond, length as m-dash]Sn-Ar<sup>Mes</sup>] (<b>3-Sn</b>), respectively. Formation of <b>3-Sn</b> proceeds <i>via</i> the niobiastannylene [(κ<sup>3</sup>-tmps)(CO)<sub>3</sub>Nb-SnAr<sup>Mes</sup>] (<b>4-Sn</b>), which was detected by IR and NMR spectroscopy. The niobium tetrylidyne complexes <b>2-Si</b>, <b>3-Ge</b> and <b>3-Sn</b> were fully characterized and their solid-state structures determined by single-crystal X-ray diffraction studies. All complexes feature an almost linear tetrel coordination and the shortest Nb-E bond lengths (<i>d</i>(Nb-Si) = 232.7(2) pm; <i>d</i>(Nb-Ge) = 235.79(4) pm; <i>d</i>(Nb-Sn) = 253.3(1) pm) reported to date. Reaction of <b>3-Ge</b> with a large excess of H<sub>2</sub>O afforded upon cleavage of the Nb-Ge triple bond the hydridogermanediol Ge(Ar<sup>Mes</sup>)H(OH)<sub>2</sub>. Photodecarbonylation of [CpNb(CO)<sub>4</sub>] (Cp = η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>) in the presence of Ge(Ar<sup>Mes</sup>)Cl afforded the red-orange chlorogermylidene complex [Cp(CO)<sub>3</sub>Nb[double bond, length as m-dash]Ge(Ar<sup>Mes</sup>)Cl] (<b>5-Ge</b>). The molecular structure of <b>5-Ge</b> features an upright conformation of the germylidene ligand, a trigonal-planar coordinated Ge atom, and a Nb-Ge double bond length of 251.78(6) pm, which lies in-between the Nb-Ge triple bond length of <b>3-Ge</b> (235.79(4) pm) and a Nb-Ge single bond length (267.3 pm). Cyclic voltammetric studies of <b>2-Si</b>, <b>3-Ge</b>, and <b>3-Sn</b> reveal several electron-transfer steps. One-electron oxidation and reduction of the germylidyne complex of <b>3-Ge</b> in THF are electrochemically reversible suggesting that both the radical cation and radical anion of <b>3-Ge</b> are accessible species in solution.","dates":{"release":"2017-01-01T00:00:00Z","publication":"2017 Sep","modification":"2025-04-07T11:16:47.181Z","creation":"2025-04-07T11:16:47.181Z"},"accession":"S-EPMC5956830","cross_references":{"pubmed":["29896377"],"doi":["10.1039/c7sc02708g"]}}