Brunner, Henri

Kauermann, H.

Klement, U.

Wachter, Joachim

Zahn, T.

Ziegler, M. L.

English

University of Regensburg Publication Server

ucts with cis-hexahydroindane framework in the hydrogen- ation of 1.  This was explained in terms of hydrogenation of the 3,3a-double bond of the intermediary dienol and not of the 3a,4-double bond (see Scheme 1, analogue A). If this were true the formation of a dienol would lead to a planarization of the symmetry center at C-3. Thus, on ad- dition of hydrogen the C3-epimer of 5 should be formed. However, this inversion is not observed. The acetate 7 obtainable from 1 is a molecule which ex- hibits the same relative stereochemistry at  the centers 3, 3a, and 7a as observed in the naturally occurring prosta- glandins. Experimental 2 :  A solution of 1 (11.1 g, 4.1 mmol) and NBS (10 g, 5.6 mmol) in CCI, (300 mL) was heated to boiling for 2.5 h. After cooling, succinimide was filtered off, the filtrate evaporated down in a vacuum, and the residue taken up in a little ether. 9.7 g of 2 (68%) crystallized out within about 12 h on cooling the filtrate in a refrigerator at ca. 0°C. Colorless crystals, m.p. 154°C; IR: 1750, 1640, 1605 cm- '  (CO); 'H-NMR: 6= 1.18 (s, 9H,  tBu), 1.52 (s, 3H,  7a-CH,), 3.58 (dd, I H ,  J1.2=10.1, J1,2,=7.6 Hz, C'-H), 5.87 (dd, J x 2  =7.4 Hz, C'-H). l H ,  J,,2=8.9, 3:  The isomeric bromide 3 can also be isolated (in smaller amounts than 10%) from the mother liquor on silica gel with ether. Colorless crystals, m.p. 132°C (etherlpetroleum ether; IR: 1745, 1640 cm- '  (CO); 'H-NMR: 6= 1.16 (s, I H, 7a-CH3), 1.24 ( s ,  9H,  fBu), 4.28 (dd, I H, J,.*= 10.0, J1.* =6.3 4 :  A solution of 2 (3.4 g, 1 mmol) and silver acetate (2 g, 1.2 mmol) in glacial acetic acid (100 mL) was heated to boiling for 3.5 h. After cooling, silver bromide was filtered off, the solvent removed in a vacuum, and the residue crystallized from ether/petroleum ether ( I  : 1); yield 1.8 g (56%). Colorless crystals, m.p. 131-132°C; IR: 3300-2400 (br.), 1750, 1710, 1690 cm-I (CO); 'H-NMR: 6 =  1.19 (s, 9H,  rBu), 1.21 (s, 1 H, 7a-CH3), 2.03 (s, 3 H ,  ace- tate), 3.90 (dd, I H ,  J1.2=11.5, J,,,.=6.5 Hz, C'-H), 6.24 (dd, l H ,  J3.2=8.5, Received: October 26, 1984 [Z 1050 IE] German version: Angew. Chem. 97 (1985) 129 Hz, C'-H), 6.04 (dd, 1 H, J3.2=5.0, J1,2,=1.2 Hz, C3-H). J3,2.=2 Hz, C3-H). Synthesis of l(C5Me5)2M~2XS3Co(C0)21 Clusters (X = P, As) and Structural Characterization of a pz,q2-AsS Ligand By Henri Brunner, Heike Kauermann, Ulrich Klement, Joachim Wachter*, Thomas Zahn, and Manfred L. Ziegler Spectroscopic investigation of the complexes 1 and 2, which were synthesized from [C5Me5(CO),Mo], and As4S4 or P4S3, revealed the possible presence of an unusual p,$- XSX-structural unit"]. Since it has so far proven impossi- ble to confirm the presence of such a unit by single-crystal X-ray structural analyses, we attempted the preparation of clusters via a secondary reaction with C O ~ ( C O ) ~  in the hope that their mode of synthesis might throw some light on the structure of 1 and 2.  T * However, according to elemental analyses and mass spectra, the diamagnetic clusters 3 and 4''' formed on reaction of 1 and 2 respectively with CO,(CO)~ surpris- ingly contained one X-atom less than expected. An X-ray structure analysis carried out on 3 showed the presence of [ I ]  Z. G. Hajos, D. R. Parrish, J. Org. Chem. 38 (1973) 3239. [21 All compounds were characterized by elemental analyses as well as 1R and NMR data. All NMR spectra were recorded in CDCI, on a 200-MHz instrument, all IR spectra in KBr. [31 L. Horner, E. H. Winkelmann, Angew. Chem. 71 (1959) 349. [41 2 can be esterified with diazomethane in ether. 2-Me-ester: colorless crystals, m.p. 121 "C (ether/petroleum ether), 'H-NMR: 6= 1.18 (s, 9H,  IBu), 1.44 (s, 3H,  7a-CH3), 3.77 (s, 3H,  ester), 3.56 (dd, I H, J1.>= 10.5, [5] We thank Dr. K. Pachler (Analytisches Zentrallabor, E. Merck Darm- stadt) for recording and discussing the 'H-NMR spectra. [61 2. G. Hajos, D. R. Parrish, E. P. Olivek, Tetrahedron 24 (1968) 2039; U. Eder, H. P. Lorenz, DOS 2320285 (7. 11. 1974), Schering AG; T. C. McKenzie, J. Org. Chem. 39 (1974) 629; R. L. Augustine, D. C. Miglio- rini, R. E. Foscante, C. S. Sodaoo, M. J. Sisbarro, ihid. 34 (1969) 1075. [7] Overall yields for all four compounds: quantitative. The product distribu- tion is variable(COI-cleavage!).-5 : colorless crystals, m.p. 118.5 "C (eth- er), IR: 3300-2500 (br), 1740, 1650, 1603 cm-I (CO); 'H-NMR: 6= 1.04 (s, 3 H, 7a-CH3), 1.14 (s, 9 H ,  tBu), 1.97 (s, 3H, acetate), 3.73 (dd, 1 H, J1,2,=7.5 Hz, C'-H), 5.06 (dd, 1 H, J3.>=9, J3,*,=7 Hz, C3-H). JI2=7.9, J ,2.=9.2 Hz, C'-H), 5.04 (ddd, IH,  J3.2=10.0, J3,2.=4.2, J3.3,=9.6 Hz, C'-H), 2.37 (dd, l H ,  J,,,3=9.6, J3,4=13.1 Hr, C'"-H), 3.44 (d, I H, J4.3r= 13.1 Hz, C4-H).-6: colorless crystals, m.p, 104°C (ether/petroleum ether), IR: 3400-2500 (br.), 1730, 1700, 1640, 1595 acetate), 2.85 (d, 1 H, J3,.,=6.8 Hz, C3"-H), 3.66 (dd, 1 H, J l  >=6.7, J, ,,=6.7 Hz, C'-H), 5.46 (m, l H ,  C'-H).-7: colorless crystals, m.p. 94°C (ether/petroleurn ether), IR: 1740, 1720 cm-'  (CO); 'H-NMR: 6= 1.03 (s, 3 H, 7a-CH3), 1.14 (s, 9 H, tBu), 1.9 (m, 1 H, C'"-H), 2.02 ( s ,  3H,  acetate), 3.66 (dd, 1 H, J1.2=7.8r J, ,,=9.2 Hz, C'-H), 4.88 (ddd, 1 H, J3*=9.8, Ji.2 =4.3, J33,9=9.2 Hz, C'-H).--8: colorless crystals, m.p. 77°C (ether/petroleum ether), 'H-NMR: 6 =  1.14 ( s ,  3H,  7a-CH3), 1.16 (s, 9 H ,  tBu), 1.94 (s, 3H,  acetate), 2.3 (in, 1 H, C3"-H), 3.81 (dd, I H, c m - l .  , I H-NMR:6=0.98 (s, 3H, 7a-CH,), 1.17 (s, 9 H ,  tBu), 1.94 (s, 3H,  J12=6.2, J12 ,=5 .4  Hz, C'-H), 5.31 (ddd, IH,  J3,~=6.1, J32,=3.4, Ji 3,* = 5.7 Hz, C3-H). [XI The methyl esters of 5 and 6 can be prepared by esterification with dia- zomethane: 5-Me-ester: colorless crystals, m.p. 119-121 "C (petroleum ether), 'H-NMR: 6= 1.05 (s, 3 H, 7a-CH3), 1.14 (s, 9H,  tBu), 1.98 ( s ,  3 H, acetate), 3.7 (s, 3 H, OMe).-6-Me-ester: colorless oil, 'H-NMR: 6=0.97 ( s ,  3H,  7a-CH1), 1.16 (s, 9 H ,  tBu), 1.91 (s, 3 H, acetate), 3.74 (s. 3H, OMe). Positions and couplings of the remaining protons as in 5 and 6 ~71. Fig. 1. Molecular structure of 3 in the crystal (ORTEP diagram). Selected bond lengths [A] and angles ["I: Mol-Mo2 2.610(1), Mol-Co 2.722(2), Mol-As 2.533(2), Mol-SI 2.517(2), Mol-S2 2.4060). Mol-S3 2.416(4), Mo2-Co 2.725(2), Co-S2 2.178(3), Co-s3 2.165(4), As-SI 2.237(3); Mo2-Mol-Co 61.4(0), Mo2-Mol-As 58.7(0), Mo2-Mol-SI 58.6(1), Mo2-Mol-S2 57.3(1), Mol-Co-SZ 57.5(1). The As and SI positions are each 50% statistically occupied by arsenic and sulfur. [*I Dr. J. Wachter, Prof. Dr. H. Brunner, Dipl.-Chem. H. Kauermann, Dr. U. Klernent Institut fur Anorganische Chemie der Universitat Universitatsstrasse 31, D-8400 Regensburg (FRG) DipLChem. T. Zahn. Prof. Dr. M. L. Ziegler lnstitut fur Anorganische Chemie der Universitlt Im Neuenheimer Feld 270, D-6900 Heidelberg (FRG) I32 0 VCH Verlagsgeselhchaft mhH, 0-6940 Weinheim, 1985 0570-0833/85/0202-0132 $ 02.50/0 Angew.  Chem. In!.  Ed. Engl.  24 (1985) No .  2 an Mo,Co-triangle bridged by two p3-sulfur ligands and a new structural unit, an q2-AsS ligand as bridge between two Mo atoms. The Ass-ligand, the two S-bridges and the Co- atom lie in a plane bisecting the molecule. The carbonyl groups are located in the plane of the three-membered ring of metal atoms (Fig. 1). Hence, 3 constitutes the first ex- ample of a molecule containing complex-stabilized arsenic monosulfide, which, in the free state, is unstable. With the proviso that there is a 50% statistical distribution of arsenic and sulfur at the As and S! sites, the As-Sl distance in 3 can be said to be 2.237(3) A, a value which corresponds to the average length of the As-S single bond in a-As4SP1. We conclude, therefore, that the new ligand has a bond or- der of 1 and functions as a 5e-donor. Furthermore, if we consider the p3-S atoms as 4e-donors and the remaining li- gands as 5e-donors (C,Me,-moieties) and 2e-donors (CO groups), then each metal atom acquires noble-gas configu- ration by formation of M-M single bonds. The experi- mentally determined metal-metal distances lend support to this conclusion. Remarkably, the Co(CO)z-fragment is incorporated ex- clusively in the q2-S2-group of 1 and 2, even though there are several sites open to attack in the ligand sphere of the starting complex. The S,-bridge over the Mo atoms is thereby enlarged to  an SCoS unit, while elimination of  X from the XSX-bridge leads to  formation of the bridging XS-ligand. This apparent lability of an Mo-X bond is confirmed by the sensitivity of 1 towards oxidation: Only the previously reported arsenic-free complexes [fCSMes)ZMo202SZ] and [(C5Me5)2M020S3] can be isolated from toluene solutions of 1 in presence of air. Received: October 10, 1984; revised: November 22, 1984 [Z 1034 IE] German version: Angew. Chem. 57 (1985) 122 CAS Registry numbers: 1, 90790-24-2; 2, 94570-20-4; 3, 94570-21-5; 4, 94570-22-6; [(C5MedzMo20S31, 94570-23-7; [ ( C S M ~ ~ ) ~ M O ~ O ~ S ~ I ,  94570-24-8 ; [Co,(CO),l, 10210-68-1. [I]  I. Bernal, H. Brunner, W. Meier, H. Pfisterer, J. Wachter, M. L. Ziegler, Angew. Chem. 96 (1984) 428; Angew. Chem. hi. Ed. Engl. 23 (1984) 438. 121 a) A mixture of 0.60 mmol 1 or 2 and 0.64 mmol C O ~ ( C O ) ~  in 50 mL toluene is stirred for 1 h (1) or 2.5 h ( 2 )  at room temperature. Chromato- graphic purification o n  Si02  with toluene/petroleum ether (1 : I )  afforded the red-brown complexes 3 and 4 in 60 and 28% yield, respectively. The complexes can he recrystallized from toluene/pentane (5 : 2).-b) IR (KBr, [cm-’I): 3 :  v(CO)=1975 (vs), 1927 ( s ) ;  4 :  v(CO)= 1982 (vs), 1932 (5). ‘H-NMR (S(CH,), CDC13): 3 :  1.88; 4 :  1.90. [3] P2,/n, a=11.529(7), b=15.348(9), c=l5.588(5)A,  f l=  107.28(3)”, V=2633.75 A’, 2 = 4 ,  Syntex P3 diffractometer (MoKa), 3 ” 5 2 9 5 5 ” ,  2490 observed reflections with 122.50(1), Patterson (Co, Mo, As, S) and Fourier methods, anisotropic refinement to R ,  =0.04. Further details of the crystal structure investigation are available on request from the Fach- informationszentrum Energie Physik Mathematik, D-7514 Eggenstein- Leopoldshafen 2, on quoting the depository number CSD 51 104, the names of the authors, and the full citation of the journal. [4l D. J .  E. Mullen, W. Nowacki, Z.  Kristallogr. Kristallgeom. KristaKphys. Krislallchem. 136 (1972) 48. [5l If a solution of 1 in toluene is stirred for 48 h in presence of air, subse- quent chromatographic work-up enables isolation of [(C5Me5)2M020S,] (green, 46% yield; IR (KBr, [cm-’I): v(Mo=O)=900 (vs), v(Mo=S)=482 (s); ‘H-NMR (&(CHI), CDCI,): 2.03, 1.96) and [(C5Mes)2M0202S2] (orange, 39”/0 yield; IR (KBr, [cm-’I): v(Mo=O)=898 (vs), [61 H. Brunner, W. Meier, J. Wachter, E. Guggolz, T. Zahn, M. L. Ziegler, Organornetallies J (1982) 1107; M. Rakowski DuBois, D. 1. DuBois, M. C. VanDerveer, R. C. Haltiwanger, Inorg. Chem. 20 (1981) 3064. v(Mo=S)=451 (w); ‘H-NMR (S(CH,), CDCI,): 2.00. Novel MoFeS Clusters from [(C5Me5)2M~ZS4] and Fe(C0)5 or Fe2(CO), By Henri Brunner, Norbert Janietz, Joachim Wachter*, Thomas Zahn, and Manfred L. Ziegler Thio-transition-metal clusters containing various metal atoms serve as model compounds, both in the catalysis of industrially important desulfurization reactions as well as in the deciphering of bioinorganic reactions. Of particular importance is the coupling of Mo and Fe with sulfur to give “heterocubanes”, among which, compounds with a Mo2FeZS4 core are still very poorly represented in the liter- ature. The first such cluster to be prepared and spectro- scopically characterized was [(C5Me5)2M~ZFe2(N0)2S41[’~. But “mixed” trinuclear clusters with a trigonal pyramidal MZM’S2 core and a p2,q2-di-(main group element) ligand are also still relatively rare[’]. MO --&- A 1 ? & 2 0 OC. F - 0 3 4 The three new diamagnetic MoFeS clusters 2-4 are formed on reaction of the complex 1 with Fe2(C0)9 in te- trahydrofuran (THF) (molar ratio 1 : 1.3). 2 and 4 are also formed in the photochemical reaction of 1 with Fe(CO), (in the molar ratio 1 :2) in THFr3”I. The composition of each product has been confirmed by elemental analysis and mass spectra. The ‘H-NMR and IR spectra[3b1 are con- sistent with the results of the X-ray structure analysis. Characteristic of the structures of 2 and 3[41 (Figs. 1 and 2) is a trigonal-bipyramidal MozFeSz core ; the Mo,Fe(CO), moiety is perpendicular to the plane of the sulfur ligands. As 48e-clusters, 2 and 3 each contain three metal-metal single bonds, consistent with the observed [*I Dr. J. Wachter, Prof. Dr. H. Brunner, N. Janietz institut fur Anorganische Chemie der Universitat Universitatsstrasse 31, D-8400 Regensburg (FRG) Dipl.-Chem. T. Zahn, Prof. Dr. M. L. Ziegler lnstitut fur Anorganische Chemie der Universitat Im Neuenheimer Feld 270, D-6900 Heidelberg (FRG) Angew. Chem. l n f .  Ed. Engl. 24 (1985) No. 2 0 VCH Verlag.~sqewll~chafr mbH. 0-6540 Weinheim, 1585 0570-0833/85/0202-0133 $ 02.50/0 133 

Synthesis of [(C5Me5)2Mo2XS3Co(CO)2] Clusters (X = P, As) and Structural Characterization of a μ2, η2-AsS Ligand

http://epub.uni-regensburg.de/23087/1/wachter46.pdf

Synthesis of [(C5Me5)2Mo2XS3Co(CO)2] Clusters (X = P, As) and Structural Characterization of a μ2, η2-AsS Ligand

Abstract

Similar works

Full text

Available Versions

University of Regensburg Publication Server

University of Regensburg Publication Server