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Article: Synthesis and Chemistry of Dithiadiazole Free Radicals [4-(4′-C5H4N)CN2S2] and [4-(3′-C5H4N)CN2S2]; X-ray Crystal Structures of [Pd3{μ-SNC(Ar′)NS–S,S′}2(PPh3)4] (Ar′ = 4′-C5H4N, 4′-C5H4NBEt3 and 3′-C5H4NBEt3)

TitleSynthesis and Chemistry of Dithiadiazole Free Radicals [4-(4′-C5H4N)CN2S2] and [4-(3′-C5H4N)CN2S2]; X-ray Crystal Structures of [Pd3{μ-SNC(Ar′)NS–S,S′}2(PPh3)4] (Ar′ = 4′-C5H4N, 4′-C5H4NBEt3 and 3′-C5H4NBEt3)
Authors
KeywordsPalladium
Dithiadiazole
Radicals
Issue Date2000
PublisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.eurjic.org
Citation
European Journal of Inorganic Chemistry, 2000, v. 2000 n. 5, p. 1045-1054 How to Cite?
AbstractTwo new 1,2,3,5-dithiadiazoles, [4-(4′-C5H4N)CN2S2] (L1) and [4-(3′-C5H4N)CN2S2] (L2), with different pyridyl groups at the 4-position were prepared. As Lewis bases, the dithiadiazoles reacted with Lewis acids via their pyridyl groups to form acid-base adducts with retention of the five-membered dithiadiazole ring. Ligands L1 and L2 reacted with excess triethylborane to give L1BEt3 and L2BEt3 (1a and 1b) and with Mn(CO)5Br to give the fac-Mn(CO)3Br(L1)2 (2a) and fac-Mn(CO)3Br(L2)2 (2b) complexes. When reacted with Pd0 complexes, namely, Pd(PPh3)4 and a mixture of [Pd2(dba)3] and dppf, the dithiadiazoles underwent ring-opening reaction by reductive cleavage of the S–S bond of the dithiadiazole ring. The resulting formation of Pd–S bonds gave the corresponding trinuclear complexes [Pd3{μ-SNC(4′-C5H4N)NS-S,S′}2(PPh3)4] (3a), [Pd3{μ-SNC(3′-C5H4N)NS-S,S′}2(PPh3)4] (3b), and [Pd3{μ-SNC(4′-C5H4N)NS-S,S′}2(dppf)2] (4) [dba = dibenzylideneacetone, dppf = 1,1′-bis(diphenylphosphanyl)ferrocene]. Complexes 3a and 3b reacted with excess triethylborane to give the corresponding acid-base adducts [Pd3{μ-SNC(4′-C5H4NBEt3)NS-S,S′}2(PPh3)4] (5a) and [Pd3{μ-SNC(3′-C5H4NBEt3)NS-S,S′}2(PPh3)4] (5b.) Complex 3a reacted with Mn(CO)5Br to give {[Pd3{μ-SNC(4′-C5H4N)NS-S,S′}2(PPh3)4][MnBr(CO)3]}n (6). The structures of 3a, 5a, and 5b were established by X-ray crystallography.
Persistent Identifierhttp://hdl.handle.net/10722/69694
ISSN
2015 Impact Factor: 2.686
2015 SCImago Journal Rankings: 1.018

 

DC FieldValueLanguage
dc.contributor.authorWong, WKen_HK
dc.contributor.authorSun, Cen_HK
dc.contributor.authorWong, WYen_HK
dc.contributor.authorKwong, DWJen_HK
dc.contributor.authorWong, WTen_HK
dc.date.accessioned2010-09-06T06:16:00Z-
dc.date.available2010-09-06T06:16:00Z-
dc.date.issued2000en_HK
dc.identifier.citationEuropean Journal of Inorganic Chemistry, 2000, v. 2000 n. 5, p. 1045-1054en_HK
dc.identifier.issn1434-1948en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69694-
dc.description.abstractTwo new 1,2,3,5-dithiadiazoles, [4-(4′-C5H4N)CN2S2] (L1) and [4-(3′-C5H4N)CN2S2] (L2), with different pyridyl groups at the 4-position were prepared. As Lewis bases, the dithiadiazoles reacted with Lewis acids via their pyridyl groups to form acid-base adducts with retention of the five-membered dithiadiazole ring. Ligands L1 and L2 reacted with excess triethylborane to give L1BEt3 and L2BEt3 (1a and 1b) and with Mn(CO)5Br to give the fac-Mn(CO)3Br(L1)2 (2a) and fac-Mn(CO)3Br(L2)2 (2b) complexes. When reacted with Pd0 complexes, namely, Pd(PPh3)4 and a mixture of [Pd2(dba)3] and dppf, the dithiadiazoles underwent ring-opening reaction by reductive cleavage of the S–S bond of the dithiadiazole ring. The resulting formation of Pd–S bonds gave the corresponding trinuclear complexes [Pd3{μ-SNC(4′-C5H4N)NS-S,S′}2(PPh3)4] (3a), [Pd3{μ-SNC(3′-C5H4N)NS-S,S′}2(PPh3)4] (3b), and [Pd3{μ-SNC(4′-C5H4N)NS-S,S′}2(dppf)2] (4) [dba = dibenzylideneacetone, dppf = 1,1′-bis(diphenylphosphanyl)ferrocene]. Complexes 3a and 3b reacted with excess triethylborane to give the corresponding acid-base adducts [Pd3{μ-SNC(4′-C5H4NBEt3)NS-S,S′}2(PPh3)4] (5a) and [Pd3{μ-SNC(3′-C5H4NBEt3)NS-S,S′}2(PPh3)4] (5b.) Complex 3a reacted with Mn(CO)5Br to give {[Pd3{μ-SNC(4′-C5H4N)NS-S,S′}2(PPh3)4][MnBr(CO)3]}n (6). The structures of 3a, 5a, and 5b were established by X-ray crystallography.-
dc.languageengen_HK
dc.publisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.eurjic.orgen_HK
dc.relation.ispartofEuropean Journal of Inorganic Chemistryen_HK
dc.subjectPalladium-
dc.subjectDithiadiazole-
dc.subjectRadicals-
dc.titleSynthesis and Chemistry of Dithiadiazole Free Radicals [4-(4′-C5H4N)CN2S2] and [4-(3′-C5H4N)CN2S2]; X-ray Crystal Structures of [Pd3{μ-SNC(Ar′)NS–S,S′}2(PPh3)4] (Ar′ = 4′-C5H4N, 4′-C5H4NBEt3 and 3′-C5H4NBEt3)en_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1434-1948&volume=&spage=1045&epage=1054&date=2000&atitle=Synthesis+and+chemistry+of+dithiadiazole+free+radicals+[4-(4%27-C5H4N)CN2S2]+and+[4-(3%27-C5H4N)CN2S2];+X-ray+crystal+structures+of+[Pd3{m-SNC(Ar%27)NS-S,S%27}2(PPh3)4]+(Ar%27+=+4%27-C5en_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.identifier.doi10.1002/(SICI)1099-0682(200005)2000:5<1045::AID-EJIC1045>3.0.CO;2-O-
dc.identifier.scopuseid_2-s2.0-0034023736-
dc.identifier.hkuros53845en_HK
dc.identifier.volume2000-
dc.identifier.issue5-
dc.identifier.spage1045-
dc.identifier.epage1054-
dc.publisher.placeGermany-

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