March 20, 1964
COMMUNICATIONS TO THE EDITOR
equilibrium thermal ~ y s t e r n s . ' ~These effects are strongly pressure dependent and become normal near the high pressure limit. This might contribute t o the observed inverse effect of dimethylmercury. Effects of this type are known not t o occur in solution. The explanation for anomalous a-effects in the cleavage of the carbon-mercury bondI5 is not obvious a t present . The demonstrated normal behavior of the methyl radical strengthens the usefulness and unambiguity of the secondary a-deuterium effect as a criterion for "unimolecular" cleavage. ( 1 4 ) F W Schneider and B. S. Rabinovitch, J A m . Chem. Soc , 86, 2365
(186.7) (15) See also M . .21 Kreevoy and B M. Eisen, J . Org C h e m . , 28, 2104
(1963).
CHEMISTRY DEPARTMENT ANDREASA. ZAVITSAS BROOKHAVEN SATIONAL LABORATORY STASLEY SELTZER UPTOS, SEIV YORK
1267
P"IO(CO)~C~H~. In structure I11 a carbon-sulfur double bond is n-bonded to the molybdenum atom and the neutral CH3SCH2 group donates three electronsI0 to the molybdenum atom in a similar manner t o the a-allyl ligand. The relationship between the metalligand bonding in CH3SCH2Mo(C0)2C6H6 (111) and the n-allyl derivative (11) is very similar to the relationship between the metal-ligand bonding in benzene-chromium tricarbonyl and thiophene-chromium tricarbonyl'l and is a further demonstration of the well-known analogy between the groupings > C=C< and >S: A similar yellow liquid manganese derivative CH3SCH2Mn(C0j4 (IV) has been obtained from Nahfn(CO), and chloromethyl methyl sulfide a t ~ 6 5 O . ~
n
H
KECEIVEDDECEMBER27, 1963
New Types of Organosulfur Derivatives of Metal Carbonyls
I
I/ I1
Sir:
H~,c=s ,CH3 Numerous unusual organosulfur transition metal OC-Mo-CO H I compounds have been obtained by reactions of various metal carbonyls and cyclopentadienylmetal carbonyls //M?\ with certain mercaptans, sulfides, disulfides. and cc c c dithietene~.?.~ Other types of organosulfur transition 0 0 0 0 111 metal compounds have been obtained from metal IV sulfides and certain acetylene derivatives. This communication describes a new and entirely different Analogous experiments with 2-chloroethyl methyl synthesis of new types of organosulfur derivatives of sulfideI2 and various metal carbonyl anions led to some metal carbonyls with metal-sulfur bonds. These surprising results. Thus, treatment of NaNn(CO), new compounds have been obtained by thermal or with 2-chloroethyl methyl sulfide in boiling tetrahydrophotochemical decarbonylation of compounds of genfuran gave a 26% yield of pale yellow d i a m a g n e t i ~ ' ~ (n = 1, 2, eral formula CH3S(CH2)nM(CO),(C6H6)~ crystalline volatile CH3SCH~CH2~Mn(CO)6, m.p. 56.5or 3; 11 = Fe [x = 2 , y = 11, Mo [x = 3 , y = 11, 58.5°.6 The infrared spectrum of this new organoor 51n [x = 5 , y = 01) without metal-sulfur bonds. manganese compound besides very strong bands a t These sulfur-containing transition metal alkyl deriva2071, 1996, and 1972 cm.-' due to the terminal metal tives, none of which has been previously reported, may carbonyl groups exhibits a very strong band at 1622 in turn be obtained from metal carbonyl anions and the cm.-', which may be assigned to an acyl carbonyl chloroalkyl methyl sulfides CH3S (CH2),C1. group suggesting structure VI rather than structure V. Thus, the sodium salt N ~ M O ( C O ) & ~reacts H ~ ~ with Reaction between N a F e ( c o ) ~ C & ~and 2-chlorochloromethyl methyl sulfide in tetrahydrofuran soluethyl methyl sulfide in tetrahydrofuran solution a t tion a t 25' to give the yellow crystalline alkyl triroom temperature yields a rather unstable orange liquid carbonyl derivative CHaSCHsMo(CO)3C6H6( I ) , m.p. indicated by analysis and other properties to be CH366-67°.6 On heating to -70' or ultraviolet irradiation SCH2CH2Fe(C0)2C6H6 (VII). Ultraviolet irradiation this tricarbonyl derivative forms the likewise yellow crystalline dicarbonyl derivative CH~SCHZMO(CO)Z- of this material in benzene solution gives a complex mixture from which the following compounds can be C6H6 in up to 60% yield, m.p. 66-67°.6.7 isolated by chromatography on alumina in benzene The infrared8 and proton n.m.r. spectra8 and close solution followed by crystallization from pentane or analogies in stoichiometry, physical properties, and ethanol of the fractions thus obtained : (1) unchanged general method of preparation to a-cyclopentadienylCH3SCH2CH2Fe(CO)zC6H6; (2) brown crystalline a-allylmolybdenum dicarbonyl (11)9 lead us to propose [CH3SFeCOC6H6Iz6( V I I I ) identical with the comstructure I11 for the dicarbonyl derivative CH3SCH2pound of this composition previously isolated in low (1) This work was supported in part by Grant AF-AFOSR-580-64 from yieldI4 from the reaction between [C6H5Fe(C0)2]2
0
the Air Force Office of Scientific Research. ( 2 ) K . B. K i n g , J . A m Chem. Soc , 85, I587 (19631, and references to previous work from various research groups cited therein. ( 3 ) A Davison, S Edelstein, R H. Holm, and A H Maki, Znorg. Chem., i n press.. (4) G N Schrauzer and V. Mayweg, J . A m . Chem. Soc , 84, 3221 (1962). ( 5 ) T . S. Piper and G. Wilkinson, J . Znorg. .Vud C h e m . , 9, 104 (1955). ( 8 ) These compounds gave satisfactory analyses for three t o six elements. Detailed analytical d a t a will be given in t h e full paper. ( 7 ) A mixture of -25Y0 CH3SCH*Mo(CO)&Ha and -75% CHsSCHtMo(C0)aCsHs exhibited a melting point of 55-60' indicating t h e melting point depression t o be small but detectable (8) Details of these spectra will he given in t h e full paper. (9) M . Cousins and M L H . Green, J . Chem. Soc , 889 (1963).
(10) Complexes 111 and 1V may possibly be regarded as derivatives of t h e unsaturated sulfonium ion HsC=.%CHs where t h e carbon-sulfur double bond is *-bonded t o t h e transition metal like a carbon-carbon double bond (11) E 0. Fischer and K . e f e l e , Ber , 91, 2395 ( 1 9 5 8 ) . (12) Although we have experienced no difficulties in handling 2~chloroethyl methyl sulfide apart from t h e usual obnoxious odor of divalent sulfur compounds, we advise caution in handling this compound due t o its probable high toxicity based o n its close chemical relationship t o bis(2~chloroethyl) sulfide, highly toxic "mustard gas." (13) From the proton n . m r spectrum. (14) An improved preparation of [CHsSFeCOCaHslz from [CsHaFe(CO)zl? and dimethyl disulfide giving a 3774 yield rather than a 9Yc yield has been developed and will be described in t h e full paper
1268
COMMUNICATIONS TO THE EDITOR
and dimethyl disulfide15; (3) [C6H6Fe(C0)2)1; (4) brown crystalline CH3SFe(Co)2C6H6 ( I x ) , m.p. 67t i 9 O 6 ; and ( 5 ) red crystalline CH3SCH2CH2COFeCOC6H6, m.p. 70°,6 exhibiting a single strong terminal and a single strong metal carbonyl band at 1934 acyl carbonyl band at 1618 cm.-' in its infrared spectrum clearly indicating structure X analogous to the structure VI proposed for CH3SCH2CH2COMn(CO)4.' The monomeric product CH3SFe(C0)2C6H6 ( I X ) is' the first example of a methylthio derivative of a transition metal where the sulfur atom does not bridge between two metal atoms. This organosulfur derivative may also be obtained in 13y0 yield from C6H5Fe(C0)zH I6 and dimethyl disulfide.6 Similar reactions of dimethyl disulfide with HAMn(CQ)6and C&.Mo(C0)3H have previously been shown to give the dimeric derivatives [CH3SMn(C0)4]2and [CH3SMo(C0)2C6H6]2.18 The chemical properties of CH3SFe(C0)2C6H6are consistent with its formulation as IX. Thus, on heating to 70' a t atmospheric pressure, gas is evolved and 'the dimeric derivative [CH3SFeCOC6H6 (VIII) may be isolated in 26% yield. Treatment of CH3SFe(C0)2C6H6with excess methyl iodide forms in an exothermic reaction yellow solid [C6H6Fe(C0)2S(CH3)2]I( X I ) , m.p. 104' dec.6 Detailed aspects of the chemistry outlined in this communication will be presented in future papers.
trans-cyclooctene has now been determined and the levorotatory enantiomer is assigned the (R)-configuration2 as shown in the Newman projection formula (1).
H H 1
(IS: 2S)-1,2-Dimethoxycyclooctane (8) was synthesized from the dextrorotatory (2R: 3R)-tartaric acid ( 2 ) and its sign of rotation was shown to be identical with that of the same diether obtained from (-)-transcyclooctene. (+)-Tartaric acid (2) was esterified3 with methanolic hydrogen chloride and the resulting dimethyl (2R: 3R)-tartrate was methylated4 with methyl iodide and silver oxide to give 3 . Lithium aluminum hydride reduction of the dicarboxylic ester (3) afforded the
TH COOH
HO
COOH
,
Mn
Mn I
\
1
I
VI
CHzCHzX
5
4 = = = = =
OH OTs
5a, X 5b, X
CN 5c, x COOCHI 5d, X I
= = = =
OH OTs
CN COOCHa
VI1
6
X
r
CHzX
cH&$0cH8 C H ~ O ~ o c H 3 C CHzCHzX ~30~ocH3 COOCHs CHzX 4a, X 4b, X 4c, x 4d, X 4e, X
n
!HzCHzSCH3
V
COOCHs
3
2
oc' 1, 'co
Vol. 86
L
XI (15) R B. King. P. M Treichel, and F G A Stone, J A m Chem. Soc., 83,3600 (1961). (16) ?r.parsd in situ from h'aFe(C0)KaHa and (CHdaCCI in tetrahydrofuran solution ' 7 (171 M I. H Green and P . L I h'agy, J . Organomefal. C h e m . , 1, 58 (1968). (18) P M Treichel, J. H Morris, and F G A. Stone, J . C h e m . S O L . 720 , (1963)
MELLONINSTITUTE R . B . KING PITTSBCRGH, PENNSYLVANIA 15213 M. B . BISXETTE RECEIVEDJANUARY 18, 1964
The Absolute Configuration of trans-Cyclooctene Szr The complete resolution of trans-cyclooctene was reported recently The absolute configuration of (1) A C Cope C R Ganellin H W Johnson J r T V Van Auken, and H J S Winkler J A m Chem Soc , 8 6 , 3276 (1963)
7
8
glycol (4a) in 62YGyield. The distilled glycol crystallized on cooling and was recrystallized from chloroformether ( I : 1) a t O o , m.p. 37-38°.6 The reaction of 4a with p-toluenesulfonyl chloride and pyridine yielded the ditosylate6 (4b, 94%). The corresponding diiodide (4e) was prepared6 from the ditosylate (4b) with sodium iodide and anhydrous acetone. Alkylation of either the ditosylate (4b) or the diiodide (4e) with acetonitrile did not give a satisfactory yield of the dinitrile ( 5 ~ ) . An alternative sequence of reactions was therefore utilized. The ditosylate (4b) was converted to (3S:4S)-3,4dimethoxy- 1,6-hexanedinitrile ( 4 ~ ) ' with sodium cyanide in dimethyl sulfoxide. Optimum yields (6578%) were obtained with a reaction time of 6 days and careful control of the temperature a t 20 f 3'. The dinitrile (4c) was converted to dimethyl ( 3 3 :4S)-3,4dimethoxyadipate (4d) by treatment with methanolic hydrogen chloride followed by hydrolysis of the bis(2) T h e nomenclature for absolute configuration used throughout is t h a t of R S. C a h n , C . K . Ingold, and V Prelog, E n p e r i e n l i a , l a , 81 (19.56). (3) A. Skrabal and L Herman, M o n f n s h . ,43, 633 (1922). (4) T . Purdie and J C Irvine, J Chem. Soc , 79, 957 (1901). ( 5 ) Posternak and S u s d had prepared the same glycol as an oil by its isolation from reduction as t h e diacetate followed by saponification of the purified diacetate with methanolic barium hydroxide. We isolated the glycol by treating t h e aluminate salt with a minimum of aqueous base and repeated washing of the filter cake with acetone as t h e glycol is sparingly soluble in ether. (6) T h . Posternak and J. P h Susz, Helv C h i m A c t o , 39, 2032 (1956) (7) Satisfactory analytical d a t a were obtained for all major intermediates in this synthesis T h e assigned structures are supported by spectral d a t a
