{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,14]],"date-time":"2025-10-14T07:01:15Z","timestamp":1760425275335,"version":"build-2065373602"},"reference-count":61,"publisher":"Wiley","issue":"40","license":[{"start":{"date-parts":[[2014,8,21]],"date-time":"2014-08-21T00:00:00Z","timestamp":1408579200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2014,9,26]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The neutral six\u2010coordinate silicon(IV) complexes <jats:bold>2<\/jats:bold> and <jats:bold>3<\/jats:bold> (mixture of <jats:italic>cis<\/jats:italic>\u2010<jats:bold>3<\/jats:bold> and <jats:italic>trans<\/jats:italic>\u2010<jats:bold>3<\/jats:bold>) were synthesized by reaction of the donor\u2010stabilized silylene bis[<jats:italic>N<\/jats:italic>,<jats:italic>N<\/jats:italic>\u2032\u2010diisopropylbenzamidinato(\u2212)]silicon(II) (<jats:bold>1<\/jats:bold>) with SO<jats:sub>2<\/jats:sub>. Compounds <jats:bold>2<\/jats:bold> and <jats:bold>3<\/jats:bold> are the first silicon(IV) complexes with chelating sulfito or dithionito ligands, and <jats:bold>3<\/jats:bold> is even the first molecular compound with a chelating dithionito ligand. Compounds <jats:bold>2<\/jats:bold> and <jats:bold>3<\/jats:bold> were structurally characterized by crystal structure analyses and multinuclear NMR spectroscopic studies in the solid state and in solution.<\/jats:p>","DOI":"10.1002\/chem.201404119","type":"journal-article","created":{"date-parts":[[2014,8,21]],"date-time":"2014-08-21T19:26:36Z","timestamp":1408649196000},"page":"12781-12785","source":"Crossref","is-referenced-by-count":24,"title":["Activation of Sulfur Dioxide by Bis[<i>N<\/i>,<i>N<\/i>\u2032\u2010diisopropylbenzamidinato(\u2212)]silicon(II): Synthesis of Neutral Six\u2010Coordinate Silicon(IV) Complexes with Chelating <i>O<\/i>,<i>O<\/i>\u2032\u2010Sulfito or <i>O<\/i>,<i>O<\/i>\u2032\u2010Dithionito Ligands"],"prefix":"10.1002","volume":"20","author":[{"given":"Konstantin","family":"Junold","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Felix M.","family":"M\u00fcck","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Claudia","family":"Kupper","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Johannes A.","family":"Baus","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Christian","family":"Burschka","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Reinhold","family":"Tacke","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2014,8,21]]},"reference":[{"key":"e_1_2_4_1_2","unstructured":"Selected reviews dealing with thermally stable silicon(II) compounds:"},{"key":"e_1_2_4_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar950192g"},{"key":"e_1_2_4_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/om7007869"},{"key":"e_1_2_4_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr900093s"},{"key":"e_1_2_4_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr100216y"},{"key":"e_1_2_4_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/om200017h"},{"key":"e_1_2_4_7_2","doi-asserted-by":"publisher","DOI":"10.1039\/C1SC00757B"},{"key":"e_1_2_4_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar300196u"},{"key":"e_1_2_4_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201203072"},{"key":"e_1_2_4_10_2","unstructured":"Selected publications dealing with thermally stable higher\u2010coordinate silicon(II) compounds containing amidinato ligands:"},{"key":"e_1_2_4_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200600647"},{"key":"e_1_2_4_11_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200600647"},{"key":"e_1_2_4_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja074019e"},{"key":"e_1_2_4_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic900204c"},{"key":"e_1_2_4_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9091374"},{"key":"e_1_2_4_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja106458p"},{"key":"e_1_2_4_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja205369h"},{"key":"e_1_2_4_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic2003035"},{"key":"e_1_2_4_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja210697p"},{"key":"e_1_2_4_19_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc31041d"},{"key":"e_1_2_4_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201200632"},{"key":"e_1_2_4_20_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201200632"},{"key":"e_1_2_4_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic301543y"},{"key":"e_1_2_4_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/om3008794"},{"key":"e_1_2_4_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201203109"},{"key":"e_1_2_4_23_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201203109"},{"key":"e_1_2_4_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201202936"},{"key":"e_1_2_4_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic401954e"},{"key":"e_1_2_4_26_2","doi-asserted-by":"crossref","unstructured":"K.Junold M.Nutz J. A.Baus C.Burschka C.Fonseca\u2005Guerra F. M.Bickelhaupt R.Tacke Chem. Eur. J.\u00ad2014 20 9319\u20139329;","DOI":"10.1002\/chem.201402483"},{"key":"e_1_2_4_27_2","doi-asserted-by":"crossref","unstructured":"K. Junold J.\u2005A. Baus C. Burschka C. Fonseca Guerra F.\u2005M. Bickelhaupt R. Tacke Chem. Eur. J.\u00ad2014; DOI:;","DOI":"10.1002\/ejic.201402685"},{"key":"e_1_2_4_28_2","doi-asserted-by":"crossref","unstructured":"K. Junold J.\u2002A. Baus C. Burschka M. Finze R. Tacke Eur. J. Inorg. Chem.\u00ad2014; accepted.","DOI":"10.1002\/ejic.201402685"},{"key":"e_1_2_4_29_2","unstructured":"Selected publications dealing with structurally characterized complexes with chelatingO O\u2032\u2010sulfito(2\u2010) ligands:"},{"key":"e_1_2_4_30_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(87)87136-X"},{"key":"e_1_2_4_31_2","doi-asserted-by":"publisher","DOI":"10.1039\/C39910000563"},{"key":"e_1_2_4_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00048a006"},{"key":"e_1_2_4_33_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(03)00701-0"},{"key":"e_1_2_4_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic070325h"},{"key":"e_1_2_4_35_2","doi-asserted-by":"publisher","DOI":"10.1021\/om3009553"},{"key":"e_1_2_4_36_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108768102003324"},{"key":"e_1_2_4_37_2","unstructured":"Recent publications dealing with higher\u2010coordinate silicon(IV) compounds:"},{"key":"e_1_2_4_38_2","doi-asserted-by":"publisher","DOI":"10.1039\/c1dt10898k"},{"key":"e_1_2_4_39_2","doi-asserted-by":"publisher","DOI":"10.1039\/C1DT11306B"},{"journal-title":"Eur.","first-page":"189","author":"Junold K.","key":"e_1_2_4_40_2"},{"key":"e_1_2_4_41_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201102815"},{"journal-title":"Eur.","first-page":"3216","author":"Wei\u00df J.","key":"e_1_2_4_42_2"},{"key":"e_1_2_4_43_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic401698a"},{"journal-title":"Eur.","first-page":"5821","author":"M\u00fcck F. M.","key":"e_1_2_4_44_2"},{"key":"e_1_2_4_45_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201301185"},{"key":"e_1_2_4_46_2","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.201300523"},{"key":"e_1_2_4_47_2","unstructured":"Treatment of1with a large excess of gaseous SO2at \u221278\u2009\u00b0C in toluene orn\u2010hexane led to the formation of a mixture of2 cis\u20103 andtrans\u20103 which co\u2010crystallized (molar ratio ca. 1:9:1)."},{"key":"e_1_2_4_48_2","unstructured":"Crystal structure analyses of2and3: Suitable single crystals were mounted in inert oil (perfluoropolyalkyl ether ABCR) and then transferred to the cold nitrogen gas stream of the diffractometer (2: Bruker D8 QUEST KAPPA PHOTON 100 CMOS MoK\u03b1radiation \u03bb=0.71073\u2005\u00c5 Montell mirror;3: Bruker Nonius KAPPA APEX II graphite\u2010monochromated MoK\u03b1radiation \u03bb=0.71073\u2005\u00c5). The structures were solved by direct methods (SHELXS\u201097) and refined by full\u2010matrix least\u2010squares methods onF2for all unique reflections (SHELXL\u201097).[13]SHELXLE was used as refinement GUI.[14]For the CH hydrogen atoms a riding model was employed. CCDC\u20101005683 (2) and \u20101005684 (3) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre viawww.ccdc.cam.ac.uk\/data_request\/cif. Selected data for2: single crystal of dimensions 0.35\u00d70.25\u00d70.15\u2005mm obtained by crystallization from toluene at \u221220\u2009\u00b0C C26H38N4O3SSi Mr=514.75 analysis at 100(2)\u2005K monoclinic space groupCc(no. 9) a=9.7158(5) b=17.7266(9) c=15.9804(7)\u2005\u00c5 \u03b2=98.195(2)\u00b0 V=2724.2(2)\u2005\u00c53 Z=4 \u03c1calcd=1.255\u2005g\u2009cm\u22123 \u03bc=0.197\u2005mm\u22121 F(000)=1104 2\u03b8max=53.46\u00b0 37859 collected reflections 5797 unique reflections (Rint=0.0433) 325 parameters 119 restraints S=1.066 R1=0.0411 [I>2\u03c3(I)] wR2(all data)=0.1111 abs. structure parameter=0.039(18) max.\/min. residual electron density= +0.910\/\u22120.410\u2005e\u2009\u00c5\u22123. Selected data for3: single crystal of dimensions 0.53\u00d70.49\u00d70.41\u2005mm obtained by crystallization from toluene at 20\u2009\u00b0C C26H38N4O4S2Si Mr=562.81 analysis at 100(2)\u2005K monoclinic space groupP21\/n(no. 14) a=9.4889(16) b=18.986(4) c=15.666(3)\u2005\u00c5 \u03b2=95.267(12)\u00b0 V=2810.4(9)\u2005\u00c53 Z=4 \u03c1calcd=1.330\u2005g\u2009cm\u22123 \u03bc=0.271\u2005mm\u22121 F(000)=1200 2\u03b8max=52.04\u00b0 35985 collected reflections 5540 unique reflections (Rint=0.0284) 352 parameters 0 restraints S=1.153 R1=0.0358 [I>2\u03c3(I)] wR2(all data)=0.0995 max.\/min. residual electron density=+0.652\/\u22120.374\u2005e\u2009\u00c5\u22123."},{"key":"e_1_2_4_49_2","unstructured":"Solution1H 13C{1H} and29Si{1H}\u2005NMR spectra were recorded at 23 (2 3) \u221240 (2) or \u221260\u2009\u00b0C (3) on a Bruker Avance 500 NMR spectrometer (1H 500.1\u2005MHz;13C 125.8\u2005MHz;29Si 99.4\u2005MHz). CD2Cl2was used as the solvent. Chemical shifts were determined relative to internal CHDCl2(1H \u03b4=5.32\u2005ppm) internal CD2Cl2(13C \u03b4=53.8\u2005ppm) or external TMS (29Si \u03b4=0\u2005ppm). Assignment of the13C\u2005NMR spectroscopic data was supported by DEPT 135 and1H 13C correlation experiments. Solid\u2010state15N and29Si VACP\/MAS NMR spectra were recorded at 22\u2009\u00b0C on a Bruker DSX\u2010400 NMR spectrometer with bottom layer rotors of ZrO2(diameter 7\u2005mm) containing ca. 200\u2005mg of sample (15N 40.6\u2005MHz;29Si 79.5\u2005MHz; external standard TMS (13C 29Si \u03b4=0\u2005ppm) or glycine (15N \u03b4=\u2212342.0\u2005ppm); spinning rate 7\u2005kHz; contact time 3 (15N) or 5\u2005ms (29Si); 90\u00b01H transmitter pulse length 3.6\u2005\u03bcs; repetitions time 7\u2005s)."},{"key":"e_1_2_4_50_2","unstructured":"Thetrans\/cisratio of the solid bulk co\u2010crystallizate3(1:10.2 crystallization at 20\u2009\u00b0C; 1:1.77 crystallization at \u221220\u2009\u00b0C) differed significantly from that of the single crystal studied (1:2.35 crystallization at 20\u2009\u00b0C) which indicated that the co\u2010crystallization process leads to differenttrans\/cisratios in the individual crystals formed."},{"key":"e_1_2_4_51_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201200745"},{"key":"e_1_2_4_51_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201200745"},{"key":"e_1_2_4_52_2","unstructured":"\u00a0"},{"key":"e_1_2_4_53_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0365110X56001601"},{"key":"e_1_2_4_54_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0567740878005981"},{"key":"e_1_2_4_55_2","doi-asserted-by":"publisher","DOI":"10.1021\/om950616a"},{"key":"e_1_2_4_56_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108767307043930"},{"key":"e_1_2_4_57_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889811043202"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201404119","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201404119","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T13:52:55Z","timestamp":1760277175000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201404119"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2014,8,21]]},"references-count":61,"journal-issue":{"issue":"40","published-print":{"date-parts":[[2014,9,26]]}},"alternative-id":["10.1002\/chem.201404119"],"URL":"https:\/\/doi.org\/10.1002\/chem.201404119","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"type":"print","value":"0947-6539"},{"type":"electronic","value":"1521-3765"}],"subject":[],"published":{"date-parts":[[2014,8,21]]}}}