New heterosiloxanes of bivalent Group 14 elements and their reactions with [Mo(CO)6]: crystal structures of [{M(μ-OBut)(OSiPh3)}2] (M = Ge or Sn) and [{Sn(μ-OBut)(OSiPh3)}2 Mo(CO)5]

Veith, Michael; Mathur, Charu; Hüch, Volker

doi:10.1039/a607153h

Cited by 36 publications

(19 citation statements)

References 18 publications

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“…Further searches for Ge(OR) 2 structures (when calixarenes and hydroxyl ligated species were removed due to inherent problems associated with these compounds for materials production) yielded two structure types: (i) monomeric Ge(OR) 2 where OR = OC(Bu t ) 3 , [49] O(CH 2 ) 2 NMe 2 , [63] (2,6-di-R)phenoxy [where R = tert -butyl (DBP), [21] tert -butyl-Me-4 [51] , 2,6- iso -propylphenyl, [43] phenyl (DPP) [45] ], (2,3,5,6-tetra-phenyl)phenoxy [45] , Ge(DPP) 2 (NMe 2 ) 2 [77] and (ii) dinuclear [(OR)Ge(μ-OR)] 2 where OR = mesityloxo (OMes) [45] and 2,6-di- iso -propyl phenoxide (DIP) [45] . Additionally, for Ge(II) siloxides, the heteroligated [(TPS)Ge(μ-OBu t )] 2 [47] and Ge(TPS) 2 {(TMS)N=P(PH) 2 ] 2 (CH 2 )} [64] have been disseminated as well as the Ge(IV) bis -OSiR 3 complex (porph)Ge(TPS) 2 (porph = 5,10,15,20-tetra kis (2-tri- iso -propysilyl)ethynyl) porphyrinato-N,N’,N”,N”’) [78] . We were also interested in the utility of thiolate derivatives as precursors for Ge(0) or single-source precursor for GeS x .…”

Section: Resultsmentioning

confidence: 99%

“…These compounds were generated through either the well-established transamination [66–71] reaction (equation 1), where Ge(NR 2 ) 2 (R = SiMe 3 ) [59, 60, 75] was substituted with a series of amines, alcohols, thiols (collectively referred to as H-L) or the often used alcoholysis exchange (equation 2) involving [Ge(OBu t ) 2 ] 2 [47, 76] . The H-L modifiers investigated in this work included N,N’-dibenzylethylenediamine (H 2 -DBED), tert -butanol (H-OBu t ), 2,6-di-methyl phenol (H-DMP), 2,6-di-phenyl phenol (H-DPP), tert -butyldimethylsilanol (H-DMBS), triphenylsilanol (H-TPS), triphenylsilanethiol (H-TPST), and benzenethiol (H-PS).…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Characterization of Germanium Coordination Compounds for Production of Germanium Nanomaterials

et al. 2009

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A series of novel germanium(II) precursors was synthesized to initiate an investigation between the precursors’ structures and the morphologies of the resulting nanoparticles. The precursors were synthesized from the reaction of Ge[N(SiMe3)2]2 or [Ge(OBut)2]2 and the appropriate ligand: N,N’-dibenzylethylenediamine (H2-DBED), tert-butanol (H-OBut), 2,6-di-methyl phenol (H-DMP), 2,6-di-phenyl phenol (H-DPP), tert-butyldimethylsilanol (H-DMBS), triphenylsilanol (H-TPS), triphenylsilanethiol (H-TPST), and benzenethiol (H-PS). The products were identified as: [Ge(μc-DBED)]2 (1, μc= bridging chelating), [Ge(μ-DMP)(DMP)]2 (2), Ge(DPP)2 (3), [Ge(μ-OBut)(DMBS)]2, (4), [Ge(μ-DMBS)(DMBS)]2 (5), Ge(TPS)3(H) (6), [Ge(μ-TPST)(TPST)]2 (7), and Ge(PS)4 (8). The Ge(II) metal centers were found to adopt a pyramidal geometry for 1, 2, 4, 5, 7, a bent arrangement for 3, and a tetrahedral coordination for the Ge(IV) species 6 and 8. Using a simple solution precipitation methodology, Ge(0) nanomaterials were isolated as dots and wires for the majority of precursors. Compound 7 led to the isolation of amorphous GexSy. The nanomaterials isolated were characterized by TEM, EDS, and powder XRD. A correlation between the precursor’s arrangement and final observed nanomorphology was proffered as part of the ‘precursor structure affect’ phenomenon.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Germanium Coordination Compounds for Production of Germanium Nanomaterials

et al. 2009

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“…It should be noted that the structural chemistry of unsymmetrical derivatives of divalent Group 14 elements has not been extensively studied [5,6]. Moreover, within this class of compounds, only a few alkoxy and aryloxy derivatives of germanium(II) and tin(II) have been structurally characterized, including [ClE 14 OBu t ] 2 (E 14 = Ge (3) [7], Sn (4) [7,8]), [(SiMe 3 ) 2 NSnOBu t ] 2 (5) [9], (SiMe 3 ) 2 NSnOAr * (Ar * = 2,6-di-tert-butyl-4-methylphenyl) (6) [10], [Ph 3 SiOE 14 OBu t ] 2 (E 14 = Ge (7), Sn (8)) [11], ArÕGeOR (Ar 0 = 2,4-di-tert-butyl-6-((dimethylamino)methyl)phenyl; R = Pr i (9), Et (10)) [ A solution of Ge(OCH 2 CH 2 NMe 2 ) 2 (1.90 g, 7.7 mmol) in THF (10 ml) was added at room temperature to a stirred solution of Ge[N(SiMe 3 ) 2 ] 2 (3.02 g, 7.7 mmol) in THF (10 ml). The reaction mixture was heated to boiling for 5 min.…”

Section: Introductionmentioning

confidence: 99%

“….141(4) Å[7], 2.153(2) and 2.156(2) Å[8]), 5 (2.168(4) and 2.173(4) Å ,Table 3,[9]), 8 (2.079(4) and 2.099(4) Å[11]), [Sn(OBu t ) 2 ] 2 (2.128(4) and 2.165(4) Å[7]), and binuclear tin(II) calix[4]arene [Bu t -calix]Sn 2 (2.141(2) and 2.167(2) Å ; 2.169(2) and 2.193(2) Å[24]). The Sn-N(SiMe 3 ) 2 bond lengths in 2 (2.147(3) and 2.143(3) Å ,Table 3) are close to those in the very sterically strained tin(II) compounds, such as [(SiMe 3 ) 2 N]Sn[C(SiMe 3 ) 2 C 5 H 4 N-2] (2.144(5) Å [25]) and [Bu t C(NCy) 2 ]Sn[N(SiMe 3 ) 2 ] (2.134(4) Å [26]).…”

mentioning

confidence: 98%

New stable germylenes, stannylenes, and related compounds

Khrustalev¹,

Portnyagin²,

Zemlyansky³

et al. 2005

Journal of Organometallic Chemistry

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“…Compound 2 was synthesized according to a procedure described earlier. 10 Commercial SnF 2 (Aldrich) was used. The NMR spectra were recorded on a Bruker AM360 (360.13 MHz for 1 H, 90.55 MHz for 13 C, and 111.92 MHz for 119 Sn) instrument in ethanol free dry CDCl 3 .…”

Section: Methodsmentioning

confidence: 99%

New stable germylenes, stannylenes, and related compounds 7. Synthesis and structures of compounds Hal—Sn—OCH2CH2NMe2 (Hal = Cl or F)

et al. 2007

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New stable divalent tin derivatives containing no bulky substituents at the metal atom, Hal-Sn-OCH 2 CH 2 NMe 2 (Hal = Cl or F), were synthesized, and their crystal structures were studied by X ray diffraction. Unlike the analogous monomeric divalent germanium de rivative Cl-Ge-OCH 2 CH 2 NMe 2 , the new compounds are centrosymmetric dimers formed via two intermolecular Sn←O coordination bonds.Earlier, 2 we have demonstrated that bidentate β di methylaminoethoxy ligands stabilize the divalent germa nium and tin compounds M(OCH 2 CH 2 NMe 2 ) 2 (M = Ge (1) or Sn (2)) in the monomeric form without steric shielding of the reactive center M by the bulky substitu ents. In the case of the germanium(II) derivatives, the presence of only one Me 2 NCH 2 CH 2 O ligand is sufficient for stabilization of the monomeric unsymmetrical com pounds XGeOCH 2 CH 2 NMe 2 (X = Cl (3) or OAc (4)). 3 In the present study, we synthesized new stable divalent tin derivatives Hal-Sn-OCH 2 CH 2 NMe 2 (Hal = Cl (5) or F (6)) analogous to the previously studied germa nium(II) derivative 3 and established their structures by X ray diffraction. Results and DiscussionDivalent tin chloro and fluoroalkoxides ClSnOCH 2 CH 2 NMe 2 (5) and FSnOCH 2 CH 2 NMe 2 (6) were prepared according to a known procedure for the synthesis of tin(II) alkoxyhalides containing no intramo lecular coordination bonds, 4-7 i.e., by the reactions of equimolar amounts of Sn(OCH 2 CH 2 NMe 2 ) 2 (2) and tin dihalides in THF at ~20 °C (Scheme 1).Compounds 5 and 6 are colorless crystalline substances unstable in the presence of even trace amounts of atmo spheric oxygen and moisture and soluble in polar aprotic organic solvents. The compositions of these compounds were determined by elemental analysis and confirmed by NMR spectroscopy.The structures of compounds 5 and 6 were studied by X ray diffraction. Unfortunately, crystals of fluoro de rivative 6 were of poor quality and, consequently, the experimental data did not allow us to discuss its structure in detail. However, the principal structure of this com pound was unambiguously established, and it is similar to that of chloroalkoxide 5. Hence, we comprehensively dis cuss only the structure of compound 5.We found that, unlike monomeric germa nium(II) alkoxychloride 3, tin(II) derivatives 5 and 6, like [N 3 SnOCH 2 CH 2 NMe 2 ] 2 (7) 8 and [(Me 3 Si) 2 NSnOCH 2 CH 2 NMe 2 ] 2 (8), 1 are centrosymmet * For Part 6, see Ref. 1. Scheme 1Hal = Cl (5), F (6)

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New heterosiloxanes of bivalent Group 14 elements and their reactions with [Mo(CO)6]: crystal structures of [{M(μ-OBut)(OSiPh3)}2] (M = Ge or Sn) and [{Sn(μ-OBut)(OSiPh3)}2 Mo(CO)5]

Cited by 36 publications

References 18 publications

Synthesis and Characterization of Germanium Coordination Compounds for Production of Germanium Nanomaterials

Synthesis and Characterization of Germanium Coordination Compounds for Production of Germanium Nanomaterials

New stable germylenes, stannylenes, and related compounds

New stable germylenes, stannylenes, and related compounds 7. Synthesis and structures of compounds Hal—Sn—OCH2CH2NMe2 (Hal = Cl or F)

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