A Metal Carbonyl Compound of Titanium¹

Abstract

Anal. Calcd. for [Co(C2H8NZ)2C~O4]C1~Hz0: C, 22.48; H,5.66; N, 17.48. Found: C,22.70; H, 5.76; N, 17.69. d-Oxalatobisethylenediamine-cobalt(II1)Iodide .-The dl-chloride, above, (12.84 9.) in water (80 ml., 65"), was shaken with silver acetate (6.4 g.) for 10 min. The silver chloride was removed and washed with hot water. To the filtrate a t 60' was added l-K[CoEDTA].2Hz0 (8.44 8.) and dissolved by shaking. Almost immediately the diastereoisomer d-[CoenzCz04]-Z-[Co(EDTA)]~ 3Hz0 commenced t o separate, and the mixture was allowed to cool slowly to room temperature. The pink-violet diastereoisomer was then collected, washed with ice-water and then ethanol and air-dried (yield, 10.7 g., [ a ]~ = +550°). Anal. Calcd. for [CO(C~H,NZ)Z(CZO~)] [CO(C~OHIZNZOS)]-3H20: C, 28.75; H, 5.13; N, 12.58. Found: C, 29.0; H , 4.91; N, 12.63.The diastereoisomer was ground up with water (50 ml.) containing potassium iodide (10 9.) and the insoluble d-iodide collected. The resolving agent was recovered from the iiltrate by adding alcohol (yield, 7.2 g., 85%). The d-iodide (7.0 g.) was recrystallized from a large volume of hot water. By standard methods using the appropriate silver salts, the chloride, bromide and sulfate were prepared. The specific rotations [ C Y ] D~ were: [CoenzC204]I, +72OO0; [CoenzCt04] Br.HZ0, $820 . [Coen2C?04] Cl.HzO, +930 ; [CoenzCz04] 2-Anal. Calcd. for [ C O ( C~H~N~)~( C~O~) ] I : C, 18.28; H, 4.09; N, 14.22. Found: C, 18.51; H , 4.16; N, 13.90. l-Oxalatobis-( ethylenediamine)-cobalt( 111) Bromide 1-Hydrate.-The filtrate from the separation of the diastereoisomer above was treated a t 60' with 50% aqueous ammonium bromide (20 ml.) and the crystalline I-bromide collected after cooling. It was recrystallized once from hot water (yield, 6.

Adventures with Substances Containing Metals in Negative Oxidation States

“…Carlo Floriani had previously shown that vanadocene monocarbonyl underwent reductive cleavage by Na metal under a CO atmosphere to give good yields of CpV(CO) 4 (eq 19) We wondered whether titanocene dicarbonyl, the first known group 4 carbonyl, would undergo an analogous reduction because no previous attempts to reduce this species had been reported. It proved to be inert under Floriani conditions (eq 19), but the addition of naphthalene afforded [CpTi(CO) 4 ] - , albeit in only 20% (unoptimized) isolated yields.…”

Synthesis and characterization of titanium tetraisocyanide complexes, [CpTi(CNXyl)4E], E=I, SnPh3, and SnMe3

“…This species was tentatively identified as ''CpTi(CO) 4 I" [16], on the basis of its reaction with Na + C 5 H 5 À , which gave small amounts of the prototypical titanium carbonyl complex [Cp 2 Ti(CO) 2 ] [23]:…”

Crystal and molecular structure of two early transition-metal dicarbonyldicyclopentadienyl complexes: (.eta.5-C5H5)2Zr(CO)2 and [(.eta.5-C5H5)2V(CO)2][B(C6H5)4]

“…As part of our continuing joint program on the formation and structure of organometallic products derived from metal carbonyls and acetylenes, we report herein on the reaction of 1 and hexafluoro-2-butyne, as well as on the results of a single-crystal X-ray crystallographic study which together with spectral measurements fully characterize the organometallic product produced as a novel titanoxane (4). butyne would lead either to a titanole (2) or to an r;2-acetylene complex (3),10 in analogy with earlier reported reactions of 1 with diphenylacetylene.8,9 Accordingly, 1 was allowed to react with an excess of hexafluoro-2-butyne in benzene solution at 55 °C in a sealed system for 16 h. Chromatography of the dark orange reaction mixture on silica gel under argon produced an orange solid, which upon crystallization from tolu-(10) Formation of a product such as 3 would be less likely under our reaction conditions, since the analogous diphenylacetylene complex was produced only under conditions in which carbon monoxide was removed as it formed.…”