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Sulfurization and Selenization of the Halfsandwich Nitrosylmetal

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Sulfurization and Selenization of the Halfsandwich Nitrosylmetal Sulfurization and Selenization of the Halfsandwich Nitrosylmetal Complexes Cp*M(CO)2NO (M = Cr, Mo) and Cp*M(NO)I2 (M = Mo, W) Max Herberhold*, Guo-Xin Jin Laboratorium für Anorganische Chemie der Universität Bayreuth, Postfach 101251, D-95440 Bayreuth Arnold L. Rheingold Department of Chemistry, University of Delaware, Newark, Delaware 19716, U.S.A. Dedicated to Prof. Dr. Dr. h. c. mult. E. O. Fischer on the occasion o f his 75 th birthday Z. Naturforsch. 48b, 1488- 1498 (1993); received June 8, 1993 Sulfido Metal Complexes, Selenido Metal Complexes, Halfsandwich Nitrosylmetal Compounds, X-Ray The photo-induced decarbonylation of Cp*Cr(CO)2NO in acetonitrile solution in the presence of excess sulfur leads to the cjWo-pentasulfido complex Cp*Cr(NO)(S5) (1 a), while in the case of limited sulfur supply the binuclear bis(//-disulfido) complex Cp*2Cr2(NO)2(/i-S2)2 (4 a) is formed preferentially. The corresponding reaction with elemental selenium produces Cp*2Cr2(NO)2(//-Se2)2 (4b), irrespective of the available amount of selenium. Photodecarbon- ylation of Cp*Mo(CO)2NO gives only the binuclear derivates Cp*2Mo2(NO)2(//-E2) (E = S (5 a), Se (5 b)) which are also obtained by treating Cp*Mo(NO)I2 with H2S or H2Se, respective­ ly. Nitrosyl loss predominates if the tungsten complex Cp*W(NO)I2 is reacted with H2S; in an argon atmosphere the products are Cp*W(S)(S2)(I) (7 a) and Cp*2W2(S)2(u-S)2 (8 a), while in air some Cp*W(NO)(S5) (3a) and the oxo compounds Cp*W(0)(S2)I (7c), Cp*2W2(Ö)2(//-S)2 (8c) and Cp*,W,(S)(0)(//-S)2 (8d) are formed. The analogous reaction with H2Se leads to Cp* W(NO)(Se5) (3b), Cp*2W2(0 )2(/z-Se)2 (9c) and Cp*2W2(Se)(O)0u-Se)2 (9d), respectively. The binuclear tungsten complexes 8a,c,d and 9c,d contain a central W(/i-E),W framework (E = S or Se) which is unaffected by air, while terminal sulfido and selenido ligands are quanti­ tatively converted into the corresponding terminal oxo ligands in the presence of air in CH2C12 or THF solution. With the preparation of Cp*2W2(0)2(//-E)2 (E = S (8c) and Se (9c)), the series of dioxo complexes containing a pair of monochalcogen bridges (E = O, S, Se, Te) has become complete. The new complexes have been characterized by their IR (v(NO)), 'H and 13C NMR (Cp*) spectra as well as by electron-impact mass spectrometry. According to the X-ray structure analyses, the binuclear compounds Cp*2Cr2(NO)2(//-S2)2 (4 a) and Cp*2Mo2(NO)2(//-Se2)2 (5 b) contain two 14-electron [Cp*M(NO)j fragments which are connected by a pair of dichalcogen (rj],tj2-E2) bridging ligands (M = Cr or Mo, E = S or Se). The central M2E2 four-membered ring is not planar, and the binuclear molecules are chiral. Introduction We have recently described [1] the halfsandwich c^c/o-pentasulfido and cjc/o-pentaselenido com­ plexes la,b, 2 a and 3a,b which contain a nitrosyl ligand in addition to a voluminous pentamethyl- cyclopentadienyl ring: Cp*M(NO)(S5) Cp*M(NO)(Se5) 1 a: M = Cr (d’green) 1 b: M = Cr (black) 2 a: M = Mo (d'green) 3 a: M = W (violet) 3 b: M = W (black) Abbreviations: Cp = ^-cyclopentadienyl, 75-C5H<; Cp' = >75-methylcyclopentadienyl, ^5-C5H4Me; Cp* = ^-penta- methylcyclopentadienyl, //5-C5Me5. These compounds with a high chalcogen to met­ al ratio (5:1) are generally obtained [1] by treating The letters a and b in the numbering system refer to sul­ fur (a) and selenium (b) complexes, respectively. the halfsandwich nitrosyl complexes Cp*Cr(NO)2I and Cp*M(NO)I2 (M = Mo, W) with either meth- * Reprint requests to Prof. Dr. M. Herberhold. anolic ammonium polysulfide solutions or, in the Verlag der Zeitschrift für Naturforschung, D-72072 Tübingen case of selenium, with hydrogen selenide solutions, 0932-0776/93/1100- 1488/$ 01.00/0 generated in situ by hydrolysis of Al2Se3. However, Dieses Werk wurde im Jahr 2013 vom Verlag Zeitschrift für Naturforschung This work has been digitalized and published in 2013 by Verlag Zeitschrift in Zusammenarbeit mit der Max-Planck-Gesellschaft zur Förderung der für Naturforschung in cooperation with the Max Planck Society for the Wissenschaften e.V. digitalisiert und unter folgender Lizenz veröffentlicht: Advancement of Science under a Creative Commons Attribution Creative Commons Namensnennung 4.0 Lizenz. 4.0 International License. M. Herberhold et al. • Halfsandwich Nitrosylmetal Complexes 1489 side-products with a lower chalcogen to metal The intermediate acetonitrile complex has been ratio (mostly 2:1) are always formed as well. An characterized before [1]. Formation of the penta- alternative route to sulfldo and selenido com­ sulfido complex 1 a appears to be favoured; it was pounds is the photo-induced decarbonylation of obtained quantitatively in the presence of excess S8 the nitrosyl complexes Cp*M(CO)2NO (M = Cr, and still isolated in appreciable amounts when less Mo, W) in the presence of excess chalcogen. How­ sulfur was available. As expected, addition of S8 or ever, only la could be prepared by this method, (NH4)2Sx (jc ~ 10) to an acetonitrile solution of 4a whereas in the cases of molybdenum and tungsten, generates 1 a. products with lower chalcogen content were again The photodecarbonylation of Cp*Cr(CO)2NO invariably formed. in the presence of various amounts of selenium We now describe sulfurization and selenization ( 1 - 10-fold excess) produced only the binuclear reactions involving the Cp* halfsandwich nitrosyl­ complex 4 b. In a similar manner irradiation of metal complexes to give products of lower chalco­ Cp*Mo(CO)2NO in the presence of excess sulfur gen content. or selenium led only to the binuclear derivatives 5 a and 5b; pentachalcogenide compounds such as lb Results and Discussion and 2 a could not be isolated, although they are 1. Photodecarbonylation of Cp*M( CO) 2NO known [1], The monomethyl-cyclopentadienyl (M = Cr, M o) in the presence of sulfur or selenium complex Cp'2Mo2(NO)2(S2)2 was also prepared. Depending on the sulfur supply, the light- induced decarbonylation of Cp*Cr(CO)2NO may lead to' either Cp*Cr(NO)(S5) (la ) or Cp*2Cr2(NO)2(//-S2)2 (4 a) preferentially. 5/8 S8 • Cp*Cr(NO)(S5) 4 a: M = Cr (black) 4 b: M = Cr (black) 1a Cr hv,-CO_ £r -CO / 5 a: M = Mo (d’red) 5 b: M = Mo (black) 0 n " V " c 0 (CH3CN) 0 n " - ch 3cn 2/8 S8 - 1 /2 Cp‘ 2Cr2(NO)2(S2)2 The spectroscopic data obtained for 4a,b and Co c0 c h 3 4a 5a,b (Table I) are in agreement with binuclear Table I. Spectroscopic data for the nitrosyl-containing complexes. Compound IR (Csl) NMR (CDC13 solution) El Mass spectra {m e [%])a v(NO) ‘H >*C M + M +-2 N O - E M + -2N O -C p* [cm-1] (S values) (Ö values) M +-N O M +-2 N O - 2 E M + —2N O -E -C p* 4 a Cp*2Cr2(NO)2(jU-S2)2 1690 1.80s 10.1 (Me) 562(12% ) 470(15% ) 367 (2%) 1669 110.8 (ring) 532 (8%) 438 (96%) 502(100% ) 4 b Cp*2Cr2(NO)2(//-Se2)2 1664 1.89s 10.9 610(30% ) 555(10% ) 1626 119.7 720 (4%) 532 (50%) 690 (40%) 5a Cp*2Mo2(NO)2(Ju-S2)2 1652 1.87s 10.3 650 (23%)b 558 (68%) 455 (6%) 1645 112.9 620(15% ) 526(10% ) 423 (32%) 590(100% ) 5 b Cp*2Mo2(NO)2Gu-Se2)2 1641 1.93 s 10.9 840 (14%)b 700 (68%) 645 (8%) 1615 111.6 810(1% ) 620(10% ) 565 (21%) 780 (30%) Cp'3Mo2(N 0 ) 2(/z-S2)2 1652 2.1 Is (Me) 14.4 (Me) 538 (20%) 446 (98%) 399(12%) 1635 5.85m (1) 98.2 1 • 508 (25%) 414(14%) 367 (70%) 5.64 m (2) 95.4 } rmS 478(100%) 5.48 m ( l) 100.8(C ) a The m/e values listed refer to the isotopes 52Cr, 98Mo, 32S and 80Se; b FD mass spectra have confirmed the molecular masses of 5 a (m/e 650.1) and 5 b (m/e 840.1). 1490 M. Herberhold et al. ■ Halfsandwich Nitrosylmetal Complexes structures. Remarkably, in all cases two nitrosyl Stretching absorptions are observed in the IR spec­ / S \ .E ' tra, both in the solid state and in solution. This in­ .w — w E S dicates that the complexes cannot be centrosym- -O metric, although only one type of Cp* ring ligand is seen in the 'H and 13C NMR solution spectra. 7 a: E = S 8a: E = E' = S 7c: E = O 8c: E = E' = O The molecular structures of 4 a and 5 b were deter­ 8d:E = S, E' = 0 mined by X-ray crystallography (see below). The El mass spectra contain the molecular ion in all If the reaction of Cp*W(NO)I2 with H,S gas cases; the primary fragmentation process appears was conducted in air, several oxo complexes to be successive loss of the two nitrosyl ligands. such as 7 c, 8 c and 8d were isolated in addition to Attempts to desulfurize the pentasulfides 2 a and the only nitrosyl complex, Cp*W(NO)(S5) (3 a) 3a using PPh3 or PnBu3 gave binuclear complexes which was formed in low yield (2%).
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