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United States Patent Office Patented Nov 3,065,250 United States Patent Office Patented Nov. 20, 1962 i 2 3,065,250 stable in air, becoming brown immediately upon contact NTRLE-METAL CARBONY, COMPLEXES with air. Dewey R. Levering, Wilisagton, Rel, assignor to Her A sample of the product was analyzed under an inert cales Powder Company, Winnington, Del, a corpora atmosphere for percent carbon, hydrogen, nitrogen and tio of Delaware molybdenum. The results of the analysis compared with No Brawing. Filled May 13, 1960, Ser. No. 28,841 the theoretical percentages for (CH3CN)Mo(CO)3 are 26 Caistas. (C. 260-429) tabulated below. The present invention relates to new and useful nitrile metal carbonyl complexes and to the method of their 10 Found ''neory preparation. More specifically, the invention relates to Percent C------------------------------------- 35.4 35.56 nitrile-metal carbonyl complexes where the metal is a Percent H. 2.4 3.0 group VI-B metal (chromium, molybdenum or tungsten) Percent N- 12.35 13.92 according to the periodic system (see Lange's Handbook Percent Mo- 32.6 31.65 of Chemistry, eighth edition, pages 56–57, 1952). Some hydrogen cyanide-metal carbonyl complexes have 5 The product was identified as (CH3CN)Mo(CO)3 been reported. However, complexes of hydrogen cyanide which is in agreement with the evolution of three moles and a group VI-B metal carbonyl have never been re of carbon monoxide per mole of molybdenum carbonyl. ported, and attempts to prepare them have been unsuc The product was insoluble in benzene, carbon tetra cessful. The present invention is based on the unforeseen 20 chloride, and water; somewhat soluble in methanol; and discovery that nitriles undergo a general reaction with soluble in acetonitrile, ethylene glycol dimethyl ether, group VI-B metal carbonyls to form new and useful tetrahydrofuran and dimethylformamide. nitrile-metal carbonyl complexes, which result from the The infrared spectra of the product was obtained and replacement of one or more carbonyl groups of the metal found to be greatly different from the spectra of carbonyl by the nitrile. Mo(CO)6. In both cases the determinations were made More particularly, the present invention relates to crys in acetonitrile. - talline, yellow to orange complexes of a nitrile and a It was found that when the exact same reaction was group V-B metal carbonyl, said complexes having the attempted under identical conditions in a sealed reaction general formula vessel, thereby preventing the release of carbon monoxide, LR(CN). IMCCO) 30 changed.the acetonitrile and molybdenum carbonyl remained un in which R is a hydrocarbon radical or a hydrocarbon radical containing as a substituent a nucleophilic group, EXAMPLE 2 i.e., a group that increases the electron availability in the This example shows that the reaction between the metal triple bond region of the nitrile group, M is a hexaco carbonyl and nitrile is an equilibrium reaction and can be ordinated atom of a metal of group VI-B of the periodic 35 readily reversed by a small partial pressure of carbon table, x is an integer from 1 to 2 inclusive, n is an integer monoxide. - from 1 to 3 inclusive, y is an integer from 2 to 5 inclusive A Sample of an acetonitrile-molybdenum carbonyl com and z is an integer from 1 to 2 inclusive, and to the plex (described in Example 1) in cyclohexane solution method of preparing such complexes which comprises was placed in a stainless steel autoclave in the absence of either (1) reacting a group VI-B metal carbonyl 40 air. The autoclave was flushed with carbon monoxide, M(CO)6) with a nitrile having the formula R(CN). and the complex was allowed to react at 3000 p.s.i.g. where R and x are as above defined, under conditions carbon monoxide pressure at a temperature of 80 C. for where carbon monoxide is removed as it is formed or (2) 6 hours. On cooling molybdenunn carbonyl and aceto reacting a preformed nitrile-metal carbonyl complex hav nitrile were recovered. ing the general formula 45 EXAMPLE 3 A reaction was conducted as in Example 1 using 5.2 R" (CN)] (M(CO), parts of molybdenum carbonyl, 7.8 parts of acetonitrile in which M, x, n, y and z are as above defined and R' is and 68.4 parts of n-heptane reaction medium. After 13 a hydrocarbon radical or a hydrocarbon radical contain hours at a reflux temperature of 72-74 C. the evolution ing as a substituent a nucleophilic group, with a nitrile 50 of carbon monoxide ceased indicating the completion of having the formula R(CN), where R and x are as above the reaction. Approximately three moles of carbon mon defined, thereby replacing the nitrile component of the oxide were evolved per mole of molybdenum carbonyl. complex with another nitrile component. During the reaction period, the reaction medium became Before describing the invention in greater detail, the 55 yellow in color and a bright yellow crystalline solid pre following examples are presented for purpose of illustra cipitated. The solid was isolated by filtration in the ab tion, parts and percentages being by weight unless other wise specified. sence of air. The product was identified as EXAMPLE 1. (CH3CN)Mo(CO) A reaction vessel fitted with a condenser and means to 60 The results of an elementary analysis are tabulated below. measure the amount of carbon monoxide evolved was charged with 5.2 parts of mobdenum carbonyl and flushed with nitrogen. Then 78.3 parts of dry acetonitrile Found Theory were added and the reaction mixture refluxed at a tem Perent C------------------------------------- 37.78 35.66 perature of 80-81. C. for 3 hours, carbon monoxide be Percent H---------------------------- - - - - 2.98 3.0 ing evolved the whole time, approximately 3 moles of 65 Percent N------------------------------------- 13.02 13.92 carbon monoxide being evolved per mole of molybdenum EXAMPLE 4 carbonyl. The Solution became yellow soon after the A reaction was conducted as in Example 1 using 5.2 mixture began to reflux and all of the molybdenum car parts of molybdenum carbonyl, 7.8 parts of acetonitrile bonyl dissolved. After removing the excess acetonitrile 70 and 39.6 parts of methanol as diluent. The reaction mix under vacuum at room temperature, there remained 5.8 ture was refluxed for 5 hours at a temperature of 65° C. parts of a yellow crystalline solid which was very un with evolution of carbon monoxide. A light yellow solu 3,065,250 3. 4. tion resulted, and after evaporation of the solvent under as (CHCHCN)Mo(CO)4. The results of an elemen vacuum, a yellow crystalline solid, identical to the com tary analysis were as follows: plex described in Example 1, was obtained. Found Theory EXAMPLE 5 A reaction vessel fitted with a condenser and means to Percent C------------------------------------- 35.5 37.75 measure the amount of carbon monoxide evolved was Percent H------------------------------------- 3.08 3.17 charged with 15.6 parts of molybdenum carbonyl and Percent N------------------------------------- 8.55 8.80 flushed with nitrogen. Then 30 parts of benzonitrile in Percent Mo----------------------------------- 32.78 30.16 68.4 parts of n-heptane were added and the reaction mix EXAMPLE 9. ture refluxed at a temperature of 101-102 C. for 14 10 hours. Carbon monoxide equivalent to 3.06 moles per In another experiment conducted in the same manner mole of molybdenum carbonyl was evolved. During the as Example 8, 15 parts of n-capronitrile was substituted reaction a yellow crystalline solid precipitated and was for the propionitrile. Refluxing was conducted at a tem isolated by filtration in the absence of air. The product perature of 101° C. A brownish yellow crystalline prod was identified as (C6H5CN)Mo(CO)3. The results of 5 uct was obtained and exhibited an infrared spectra typical an elementary analysis were as follows: of a nitrile-molybdenum carbonyl complex. EXAMPLE 10 Found Theory A reaction was conducted as in Example 1 using 5.2 20 parts of molybdenum carbonyl, 11.7 parts of p-methyl Percent C------------------------------------- 58.69 58.90 Percent H. 3.18 3.09 benzoinitrile and 68.4 parts of heptane as the reaction Percent N.-- 8.4 S. 60 medium. After refluxing at a temperature of 101° C. Percent Mo- 20.67 19.64 for 9 hours, the reaction was stopped. Carbon monoxide equivalent to 2.1 moles per mole of molybdenum car EXAMPLE 6 25 bonyl was evolved. During the reaction a golden crys Molybdenum carbonyl (5.2 parts) was charged to a talline solid precipitated and was isolated by filtration in reaction vessel as described in Example 1. Then 9.5 the absence of air. The product was identified as parts of adiponitrile dissolved in 68.4 parts of heptane (CH3CHCN) 2.Mo(CO ) 4. were added and the reaction mixture refluxed at a tem 30 perature of 100-101° C. for about 23 hours. During The results of an elementary analysis were as follows: this time, an amount of carbon monoxide equivalent to 3.1 moles per mole of molybdenum carbonyl was evolved. Found Theory The reaction mixture separated into two phases during Percent C------------------------------------- 54.18 53.34 the reaction, the lower phase of which crystallized on 35 Percent H------------------------------------- 3.32 3.13 cooling. A yellow crystalline product was removed by Percent N------------------------------------- 6, 19 6.22 filtration in the absence of air. The product was identi Percent Mo----------------------------------- 22.2 21.33 fied as INC(CH2)4CNIMo(CO)3. The results of an elementary analysis were as follows: EXAMPLE 1.
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