71639-57-1

Basic information

• Product Name: [(C₅H₅)2Ti]2((CH₃C₆H₄N)2C)2
• CAS NO: 71639-57-1
• Molecular Weight: 800.718
• Mol File: 71639-57-1.mol

Chemical Properties

• CAS DataBase Reference: [(C₅H₅)2Ti]2((CH₃C₆H₄N)2C)2(CAS DataBase Reference)
• NIST Chemistry Reference: [(C₅H₅)2Ti]2((CH₃C₆H₄N)2C)2(71639-57-1)
• EPA Substance Registry System: [(C₅H₅)2Ti]2((CH₃C₆H₄N)2C)2(71639-57-1)

Safety Data

• Hazardous Substances Data: 71639-57-1(Hazardous Substances Data)

Upstream product

• 726-42-1 di-p-tolylcarbodiimide 

Downstream Products

• 75197-52-3 [(C₅H₅)2Ti]2((CH₃C₆H₄N)2C)2⁽²⁺⁾*2C₂(CN)4^(1-)=[(C₅H₅)2Ti]2(((CH₃C₆H₄N)2C)2)(C₂(CN)4)2 

Relevant articles and documents

Reactions of group 4 metallocene alkyne complexes with carbodiimides: Experimental and theoretical studies of the structure and bonding of five-membered hetero-metallacycloallenes

The reaction of the low-valent metallocene(II) sources Cp 2Ti(n2-Me3SiC2SiMe3) (7) and Cp2Zr(py)(n2-Me3SiC2SiMe 3) (11, Cp = n5-cyclopentadienyl, py = pyridine) with carbodiimides RN=C=NR (R = Cy, i-Pr, p-Tol) leads to the formation of five membered hetero-metallacycloallenes Cp2M{Me3SiC=C= C[N(SiMe3)(R)]-N(R)} (9M-R) (M = Ti, R = i-Pr; M = Zr, R = Cy, i-Pr, p-Tol). Elimination of the alkyne (as the hitherto known reactivity of titanocene and zirconocene alkyne complexes would suggest) was not observed. The molecular structures of the obtained complexes were confirmed by X-ray studies. Moreover, the structure and bonding of the complexes 9Zr-Cy and 9Zr-p-Tol was investigated by DFT calculations.(Figure Presented)

Metal-promoted C-C bond formation from one-carbon functional groups: Modeling study for reductive coupling of carbon dioxide

Bis(η5-cyclopentadienyl)dicarbonyltitanium(II), Cp2Ti(CO)2 (Cp = η5-C5H5), undergoes an oxidative addition by two molecules of diethyl ketomalonate (DEKM) with loss of the two CO groups and formation of the symmetric metallacycle Cp2Ti-O-C(R2)-C(R2)-O (I) (R = CO2C2H5). The pinacol-like structure of the ligand O,O′ bonded to titanium(IV) is shown by the NMR spectrum and confirmed by the X-ray analysis. The overall structure is that found for other Cp2Ti complexes, where the metal bonds a bidentate chelating ligand. The chelate ring has a gauche conformation, the carbon atoms being displaced by 0.18 A? on opposite sites from the Ti,O,O′ plane. p-Tolylcarbodiimide (p-TCD) is reductively coupled by Cp2Ti(CO)2 to tetra-p-tolyloxalylamidine, which acts as a dinucleating ligand bonding two Cp2Ti units, containing titanium in the +3 oxidation state (1.74 μB per titanium at 293 K) [Cp2Ti(p-TCD)]2 (II). The nature of the ligand, whose resemblance with other electronically delocalized systems is noteworthy, was clarified by an X-ray analysis. The C-N distances in the metallacycle rings have been, practically, found identical; the mean value of 1.331 (3) A? indicates a significant double-bond character. The dinucleating ligand, except for the p-tolyl groups, is perfectly planar with the two titanium atoms displaced by 0.34 A? in the opposite sites of the ligand plane. Iodine converts complex II to the corresponding diamagnetic titanium(IV) compound [Cp2Ti(p-TCD)]2(I3)2. The oxidation of II carried out with tetracyanoethylene (TCNE) affords a probable charge-transfer complex, [Cp2Ti(p-TCD)]2(TCNE)2, containing the radical anion TCNE-·, the presence of which is deduced from the IR spectrum (νCN(Nujol) = 2145 (s) and 2185 (ms) cm-1) and from the magnetic moment suggesting the presence of two unpaired electrons per unit. A mechanism is proposed for this rather unusual metal-promoted reductive coupling of DEKM and p-TCD. Crystallographic details for complex I: space group C2/c (monoclinic); a = 8.264 (1) A?, b = 30.455 (3) A?, c = 11.612 (1) A?, β = 96.33 (1)°, V = 2904.7 A?3, Z = 4, Dcalcd = 1.311 g cm-3. The final R factor is 0.068 for 1342 observed independent reflections. Crystallographic details for complex II: space group P1 (triclinic); a = 12.408 (1) A?, b = 10.449 (1) A7ring;, c = 8.179 (1) A?, α = 103.56 (1)°, β = 94.29 (1)°, γ = 94.23 (1)°, V = 1023.4 A?3, Z = 1, Dcalcd = 1.299 g cm-3. The final R factor is 0.061 for 3468 observed independent reflections.