Crystal structure and Moessbauer spectrum of [2]-ferrocenophanethiazine 1,1-dioxide

Abramovitch, R. A.; Atwood, Jerry L.; Good, Mary L.; Lampert, Benjamin A.

doi:10.1021/ic50154a045

Cited by 31 publications

(10 citation statements)

References 5 publications

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“…-2(4) C30 37( 4) 40 (3) 44 (3) 1 (3) -1 (3) -3(3) C31 39 (4) 38 (3) 71 ( 4 78 ( 4) 67 (3) 59 (3) -3(3) -25 (3) 0(2) 0(3) 77 (3) 37 (2) 46 (2) 2( 2) 11 (2)…”

Section: Determination Of the Absolute Configurationunclassified

Absolute configuration of organometallic compounds. 4. X-ray determination of the structure and absolute configuration of (-)579-(.eta.5-C5H5)Fe(CO)[P(C6H5)3]COOC10H19

Reisner¹,

Bernal²,

Brunner³

et al. 1978

Inorg. Chem.

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The structure and the absolute configuration of (-)s79-(75-C5H5)Fe(CO)[P(C6H5)3]COOC10H19 (C10H19 = menthyl) have been determined by single-crystal x-ray diffraction methods using data acquired by a computer-controlled diffractometer and Bijvoet's technique. The substance crystallizes in the orthorhombic system, space group P2,2121, with cell constants of a = 11.221 (4), b = 14.817 (7), and c = 18.958 (3) Á. The observed and calculated densities are 1.25 (2) and 1.25 g/cm3 (for Z = 4 molecules/unit cell). The Fe-(i)5-C5H5) fragment has normal distances and angles and the Cp ring is planar, as expected. The Fe-P(C6H|)3 group has stereochemical parameters which are well within the values found in the literature (i.e., Fe-P = 2.214 (2) A, P-C = 1.830 (6), 1.838 (4), and 1.853 (6) Á), and the dihedral angles of the three phenyl rings are canted at arbitrary values dictated by packing. The most important features of the stereochemistry of the molecule are the following: (1) the Fe-C(C=0) and C=0 distances are, respectively, 1.670 (7) and 1.206 (9) Á. . The former is the shortest iron to carbonyl carbon distance observed thus far. (2) The Fe-ester fragment shows a large angular distortion at the C atom such that Fe-C=0 = 132.1 (5), Fe-C-OC10Hi9 = 117.7 (4), and 0=C-O = 108.8(5)°. Concomitant with this distortion is a shortening of the Fe-C(ester) bond to 1.825 (6) Á. Both of these observations point to an enhanced r-bonding interaction between the iron atom and the carbons of the carbonyl and ester group. When the current rules for ranking groups are applied, the configuration at the iron atom is specified to be 5.

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“…-2(4) C30 37( 4) 40 (3) 44 (3) 1 (3) -1 (3) -3(3) C31 39 (4) 38 (3) 71 ( 4 78 ( 4) 67 (3) 59 (3) -3(3) -25 (3) 0(2) 0(3) 77 (3) 37 (2) 46 (2) 2( 2) 11 (2)…”

Section: Determination Of the Absolute Configurationunclassified

Absolute configuration of organometallic compounds. 4. X-ray determination of the structure and absolute configuration of (-)579-(.eta.5-C5H5)Fe(CO)[P(C6H5)3]COOC10H19

Reisner¹,

Bernal²,

Brunner³

et al. 1978

Inorg. Chem.

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“…The largest family of such [2]FCPs are those of type C , which were prepared through dilithiation of (Me 5 C 5 )Fe(C 5 H 5 ), followed by salt-metathesis reactions with the respective element halides ( C with ER x = SiCl 2 , S, SiMe 2, GeR 2 , SnR 2, PbPh 2, PAr, ZrCp 2 ). However, the first known unsymmetrically bridged [2][2]FCP, the thiaaza[2]ferrocenophane F (R = H), was already reported in 1969 and synthesized by a photolysis of the azide precursor FcSO 2 N 3 (Fc = (C 5 H 4 )Fe(C 5 H 5 )) . Other nitrogen-bridged FCPs are known but, due to an increased number of bridging elements, are insufficiently strained and had been investigated in a context different from ROP. , Our design idea behind aza[2]ferrocenophanes stemmed from the speculation that, in contrast to symmetrically bridged [2]FCPs ( B ; Chart ), a polar diatomic bridging moiety will be prone to react with polar reagents; hence, such species might be polymerizable by cationic or anionic initiators.…”

Section: Introductionmentioning

confidence: 99%

[n]Ferrocenophanes (n = 2, 3) with Nitrogen and Phosphorus in Bridging Positions

2016

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The in situ prepared dilithio derivative of the known species 1-bromo-1'-(trimethylsilylamino)ferrocene (1) reacted with tBuPCl2 to form the first example of a [2]ferrocenophane ([2]FCP) bridged by nitrogen and phosphorus (2). Sulfurization of 2 followed by column chromatography on silica gel gave the expected [2]FCP with a tBu(S)PN(SiMe3) bridging moiety (3a) and its desilylated counterpart with a tBu(S)PNH bridging moiety (3b). The molecular structure of 3b was determined by single-crystal X-ray analysis (α = 18.40(11)°). Using a common synthetic methodology, two new 1-amino-1'-bromoferrocene derivatives were prepared, one species with a PhCH2 (6a) and another with a tBuCH2 group (6b) on nitrogen. Dilithiation of 6a followed by addition of tBuPCl2 gave a mixture of three constitutional isomers: the targeted [2]FCP (7a), the 1,1'-disubstituted ferrocene derivative (tBuPH)(PhCH═N)fc (8a), and the [3]FCP bridged by a (NH)(CHPh)PtBu moiety (9a). NMR spectroscopy revealed that 8a is the precursor for 9a. The salt-metathesis reaction of the dilithio derivative of 6b with tBuPCl2 exclusively gave the 1,1'-disubstituted ferrocene derivative (tBuPH)(tBuCH═N)fc (8b), which does not isomerize to the respective [3]FCP. DFT calculations at the M06/6-311+G(d,p) level were used to better rationalize these unexpected results.

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“…6 The addition of ferrocene to the solution before thermolysis had a slight beneficial effect upon the yields of products but no change in their nature was observed. This contrasts (as do most of the above results) with the behavior of o-benzenedisulfonyl azide, which, on thermolysis in benzene, gives both o-benzenedisulfonylanilide and benzenesulfonylanilide-2-sulfonamide.…”

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confidence: 98%

“…3, 1976 497tube was recrystallized from benzene-light petroleum (bp 60-110') to give golden yellow plates of ferrocenyl ferrocenethiolsulfonate, begins to darken at 180' and melts at 194-195' (dec): ir (KBr) 1320 (s), 1120 cm-l(8); NMR (CDC13)6 4.40 (m, 9 H),4.32 (m, 2 H),4.21(6, 5 H), and 4.18 (m, 2 H); mass spectrum (70 eV) m/e (re1 intensity) 467 (21, 466 (Me+, 71, 402 (52), 306 (221, 304 (24), 272 (24), 233 (21), 218 (36), 217 (loo), 186 (29), 153 (39), 121 (40), 56 (31). Anal.…”

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confidence: 99%

“…5 A number of interesting reactions were observed, particularly with the ortho derivative, decomposition of which led, among others, to the generation of benzyne, as well as to the loss of one of the sulfonyl azide moieties. It was, therefore, decided to study the behavior of ferrocene-1,l'-disulfonyl azide (6). Among the possibilities were that a ferrocenophane derivative related to 4 would be formed and that the second sulfonyl azide group would react with solvent [formation of a dibridged species such as A was considered unlikely since models showed (and x-ray analysis has since confirmed6) that the two cyclopentadienyl rings were certainly not parallel in 4).…”

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Ferrocene-1,1'disulfonyl azide and 2,4,6-trimethylpyridinium ferrocenesulfonyl ylide. Synthesis and decomposition

Abramovitch¹,

Holcomb²

1976

J. Org. Chem.

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the end point was not distinct. The products were stored (frozen) in serum bottles under argon. Preparation of 3-Aryl-5,5-dimethylthiazolidine-2-thione~(6a-c). The general method5 was to reflux a mixture of the thiol (3.0 mmol) or disulfide (1.5 mmol), 10 N NaOH (0.30 ml), CSz (7 mmol), and ethanol (10 ml) for 24 hr (argon), add water (3-4 ml), and chill. The crystalline derivative was filtered, waehed (cold MeOH, then H20), and recrystallized from the same ethanolwater mixture prior to analysis. The yields listed are for the crude products. Use of the disulfides 3a and 3c led to similar (or higher) yields of the identical 6 (melting point and mixture melting point). 3-Phenyl-5,5-dimethylthiazolidine-2-thione (sa): colorless plates (45%), mp 114-115'. Anal. Calcd for CllHnNSZ: c , 59.15; H, 5.86; N, 6.27. Found: C, 58.80; H, 5.87; N, 6.17. 3-(p-Chlorophenyl)-5,5-dimethylthiazolidine-2-thione (6b): colorless needles (34%), mp 111-111.5°. Anal. Calcd for C11H12ClNS2: C, 51.25; H, 4.69; N, 5.43. Found: C, 51.34; H, 4.81; N, 5.81. 3 4 p-Dimethylaminophenyl)-5,5-dimethylthiazolidine-2thione (6c): pale yellow needles (79%), mp 156-157O (lit5 157-158O). Nickel(I1) Complex of 5. A solution of 5 (1 mmol) in MeOH (4 ml) was added to a warm solution of Ni(OAc)~.4H20 (1 mmol) in MeOH (8 ml). The solid, which separated immediately, was filtered, washed (MeOH), and vacuum dried (1 hr at 50') to give 188 mg (61.4%) of the tan-pink crystalline complex. Its ir spectrum exhibited bands a t 3220 and 3270 cm-l (sh) (coordinated NH). Anal. Calcd for CloHZ2N2SzNi.%H20: C, 39.75; H, 7.67; N, 9.27. Found: C, 39.67; H, 7.85; N, 9.59. Registry No.-la, No attempt was made to optimize yields. (17) We have no explanation as yet for the uptake of less l2 by those thiols containing aliphatic amino groups.Photolysis of ferrocene-1,l'-disulfonyl azide in various solvents and a t different wavelengths gave 1'-sulfamylferrocenesulfonyl azide and ferrocene-1,l'-disulfonamide. The thermolysis products depended on the solvent used. In cyclohexane, 1'-sulfamylferrocenesulfonyl azide, ferrocene-1,l'-disulfonyl azide, N,N'dicyclohexylferrocene-1,l'-disulfonamide, 1'-(N-cyclohexylsulfamy1)ferrocenesulfonyl azide, and 1'-(N-cyclohexylsulfamy1)ferrocenesulfonamide were obtained. In benzene, products both of kinetic (azepine) and thermodynamic control (anilide) were formed but disubstitution did not occur. In mesitylene, the dimesitylamide was obtained. No intramolecular cyclization products were ever detected. 2,4,6-Trimethylpyridinium ferrocenesulfonyl ylide did not undergo photolysis but did thermolyze to ferrocenesulfonamide and sym-collidine. Again no ferrocenophane was formed.

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Crystal structure and Moessbauer spectrum of [2]-ferrocenophanethiazine 1,1-dioxide

Cited by 31 publications

References 5 publications

Absolute configuration of organometallic compounds. 4. X-ray determination of the structure and absolute configuration of (-)579-(.eta.5-C5H5)Fe(CO)[P(C6H5)3]COOC10H19

Absolute configuration of organometallic compounds. 4. X-ray determination of the structure and absolute configuration of (-)579-(.eta.5-C5H5)Fe(CO)[P(C6H5)3]COOC10H19

[n]Ferrocenophanes (n = 2, 3) with Nitrogen and Phosphorus in Bridging Positions

Ferrocene-1,1'disulfonyl azide and 2,4,6-trimethylpyridinium ferrocenesulfonyl ylide. Synthesis and decomposition

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