135394-63-7

Upstream product

• 591-51-5 phenyllithium 
• 199620-14-9 chromium⁽⁰⁾ hexacarbonyl 
• 148538-99-2 ([2-[(dimethylamino)methyl]phenyl]hydrosilanediyl)chromium⁽⁰⁾ pentacarbonyl 
• 135394-61-5 SiCl₂(C₆H₄CH₂N(CH₃)2)(C₆H₅) 
• 180469-20-9 (C₆H₄CH₂N(CH₃)2)SiCl₃ 
• 70318-28-4 [pentacarbonyl Cr]^(2-) 
• 135394-61-5 2-((dimethylamino)methyl)phenyl(phenyl)dichlorosilane 

Relevant academic research and scientific papers

Unexpected reactivity of functionalized lewis base stabilized silanediyl transition metal complexes toward organolithium nucleophiles

(Organosilanediyl)chromium(0) pentacarbonyl complexes, [2-(Me2NCH2)C6H4]RSi=Cr(CO) 5 (R = Me, Ph, t-Bu, Ph-C≡C-, Me3Si-C≡C-), are obtained in good yield through the coupling reactions of (arylhydrogenosilanediyl)chromium(0) pentacarbonyl complex [2-(Me2NCH2)C6H4]HSi=Cr(CO) 5, with the corresponding organolithium nucleophiles. Unexpectedly, the chloro- and bromosilanediyl complexes [2-(Me2NCH2)C6H4]-XSi=Cr(CO) 5 (X = Cl, Br) are unreactive, but the fluorosilanediyl complex is even more reactive than the hydrogenosilanediyl complex with methyllithium. Possible geometries of the intermediate resulting in frontside attack of the nucleophile upon a zwitterionic silicon species are discussed.

New investigations in silanediyl complex chemistry: Synthesis, structure, and bonding of 1-metalla-2-sila-1,3-dienes

The synthesis and chemical behavior of the intra- and intermolecular donor-stabilized silanediyl complexes (C6H4CH2NMe2-2)(Cl)Si=MLn (4, MLn = Cr(CO)5 5, MLn = Fe(CO)4), (C6H5HC=CH)(Cl)Si=MLn·OP(NMe 2)3 (21, MLn = Cr(CO)5; 22, MLn = Fe(CO)4), and (C6H5-HC=CH)(C6H5)Si=Fe(CO) 4·OP(NMe2)3 (23) is discussed. Nucleophilic substitution of the chloro atom in compounds 4 and 5 by different nucleophiles leads to a great variety of further functionalized silanediyl complexes of the type (C6H4CH2NMe2-2)(R)Si=MLn (MLn = Cr-(CO)5: 7, R = CH3; 9, R = C6H5; 11, R = P(C6H5)2; 13, R = CH=CH2. MLn = Fe(CO)4: 14, R = CH=CH2; 15, R = CH3). Moreover, the 1-metalla-2-sila-1,3-dienes (C6H4CH2NMe2-2)-(H 2C=CH)Si=MLn (13, MLn = Cr(CO)5; 14, MLn = Fe(CO)4) can be prepared by treatment of the hypervalent dichlorosilane (C6H4CH2NMe2-2)(H 2C=CH)SiCl2 (19) with the carbonylate dianions MLn2- (2, MLn = Cr(CO)5; 3, MLn = Fe(CO)4). Additionally, compounds of the latter type are accessible by photochemical coupling reactions of the pentavalent silane (C6H4-CH2NMe2-2)(CH 3)SiH2 (16) with the transition-metal carbonyls Cr(CO)6 (17a), Fe(CO)5 (17b), and (η5-C5H5)Mn(CO)3 (17c), respectively. The intermolecular donor-stabilized 1-metalla-2-sila-1,3-dienes 21-23 can be prepared by the reaction of tetravalent dichlorosilanes [(R)-(H)C=CH](R′)SiCl2 (20a, R = H, R′ = Cl; 20b, R = R′ = C6H5) with the carbonylmetalates 2 and 3 and in the presence of OP(NMe2)3.

Novel inter- and intra-molecular donor-stabilized 1-metalla-2-sila-1,3-dienes

The synthesis of the inter- and intra-molecular donor-stabilized 1-metalla-2-sila-1,3-dienes Cl(H2C=CH)Si=MLn·OP(NMe2)3 [MLn = Fe(CO)4 3a, Cr(CO)5 3b], Ph(PhHC=CH)Si=Fe(CO)4

Lewis base stabilized transition metal complexes of divalent silicon species

A direct photochemical synthesis of silanediyl-iron tetracarbonyl complexes Ph2Si(B)=Fe-(CO)4 [B = 1,3-dimethylimidazolidinone (DMI) or hexamethylphosphoric triamide (HMPA)] is described. The Lewis base character of DMI is strong eno

Reversible intramolecular base stabilization in silylene (silanediyl) complexes: Surprising reactivity for silylene coordination compounds with a dynamic N?Si?N bond

The silane [2-(Me2NCH2)C6H4] 2SiCl2 (7) shows a new dynamic N?Si?N "flip-flop" coordination mode below Tc = 233 K (ΔG? = 46.5 (±0.5) kJ mol-1) with both amine donors displacing each other. 7 is pentacoordinated in the solid state; crystal data: orthorhombic, Pbca, a = 13.802(1) A?, b = 17.908(1) A?, c = 15.544(2) A?, Z = 8. Reaction of the silanes C6H5[2-(Me2NCH2)C6H 4]SiCl2 (6), 7, and [2-(Me2NCH2)-5-(t-C4H9)C 6H3]2SiCl2 (8) with chromiumpentacarbonyl-metallate yields the silanediyl complexes [2-(Me2NCH2)C6H4]C6H 5Si=Cr(CO)5 (11), [2-(Me2-NCH2)C6H4] 2Si=Cr(CO)5 (12), and [2-(Me2NCH2)-5-(t-C4H9)C 6H3]2Si=Cr(CO)5 (13); [2-(Me2-NCH2)C6H4]HSi=Cr(CO) 5 (14) was obtained by photolytic methods. Silanediyl complexes with one chelating donor show a rigid coordination of the donor to silicon which can be lifted at higher temperatures (95°C for 11, ΔG? = 80.4 (±0.5) kJ mol-1). A single crystal X-ray structure determination of 11 reveals a CrSi bond distance of 2.409(1) A? and a N→Si bond length of 1.991(2) A?. Crystal data: triclinic, P1, a = 9.401(1) A?, b = 10.207(1) A?, c = 11.586(1) A?, Z = 2. Silanediyl complexes with two intramolecular donor functions feature a dynamic "flip-flop" coordination of the amine groups to silicon. Both (dimethylamino)phenyl groups in 12 and 13 can be detached from silicon under liberation of a three-coordinate silicon atom at Tc = 58°C (VT-1H-NMR), ΔG? = 67.1 (±0.5) kJ mol-1 for 12 and Tc = 61°C, ΔG? = 70.1 (±0.5) kJ mol-1 for 13. A single crystal X-ray structure determination of 12 gives 2.408(1) A? for the Si-Cr bond length and 2.046(2) A? for the N1-Si dative bond (the second contact N2-Si has a nonbonding distance of 3.309 A?; the sum of bond angles at silicon amounts to 351.3°). Crystal data: triclinic, P1, a = 9.531(1) A?, b = 10.339(1) A?, c = 11.676(1) A?, Z = 2. The donor in 12 has been functionalized at the nitrogen atom by protonation or complexation with BF3. Photolysis of 12 and 13 leads to a 1,2-amine shift of one donor from silicon to the metal with loss of CO. The product [2-(Me2NCH2)C6H3][2-(Me 2NCH2)C6H3]Si=Cr(CO)4 (20) has been characterized by a single crystal X-ray structure determination and has a bond distance Cr-Si 2.3610(4) A? and N1-Si 1.981(1) A?. Crystal data: monoclinic, P21/c, a = 10.344(5) A?, b = 11.761(3) A?, c = 18.96(1) A?, Z = 4. Furthermore, the silanediyl complex 12 has been immobilized on silica gel. IR and UV spectroscopy and 13C CPMAS NMR provide evidence for the fixation of (silica-O-)[2-(HNMe2CH2)C6H 4][2-(Me2NCH2)C6H 4]Si=Cr(CO)5 (22) to the surface via the silicon atom. Reaction of 13 with H2O leads to (HO)[2-(HNMe2CH2)C6H4][2-(Me 2NCH2)C6H4]Si-Cr(CO)5 (23) which has a structure similar to 22 with a Cr-Si bond length of 2.469(2) A?. The dimethylamino or dimethylammonium substituent is pointing away from the silicon atom forming hydrogen bridges between N1?HO?HN2; crystal data: monoclinic, P21/n, a = 13.198(2) A?, b = 17.017(2) A?, c = 17.066(1) A?, Z = 4.