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New Inorganic Metallacycles and the First Six‐Membered Covalent “True” Heterocycle – Oxidation of RC(E)NHPPh 2 (E = O or S; R = H 2 N, Ph, or Py) with O, S, or Se to Give RC(E)NHP(E′)Ph 2 (E′ = O, S, Se) and Their Coordination Chemistry
Author(s) -
Birdsall David J.,
Green Jason,
Ly Tuan Q.,
Novosad Josef,
Necas Marek,
Slawin Alexandra M. Z.,
Woollins J. Derek,
Zak Zdirak
Publication year - 1999
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199909)1999:9<1445::aid-ejic1445>3.0.co;2-s
Subject(s) - chemistry , deprotonation , ring (chemistry) , zinc , ionic bonding , medicinal chemistry , potassium , stereochemistry , crystallography , ion , organic chemistry
Direct oxidation of PhC(O)NHPPh 2 , H 2 NC(S)NHPPh 2 , (C 5 H 4 N)C(S)NHPPh 2 with O 2 , S 8 , or Se gives [PhC(O)NHP(O)Ph 2 ] ( 1 ), [H 2 NC(S)NHP(S)Ph 2 ] ( 2 ), [H 2 NC(O)NHP‐(S)Ph 2 ] ( 3 ), [PhC(O)NHP(S)Ph 2 ] ( 4 ), [(C 5 H 4 N)C(S)NHP(S)Ph 2 ] ( 5 ), and [H 2 NC(S)NHP(Se)Ph 2 ] ( 6 ). Deprotonation of 1 , 2 , 4 – 6 with potassium tert‐ butoxide gives K[PhC(O)NP(O)Ph 2 ] ( 7 ), K[H 2 NC(S)NP(S)Ph 2 ] ( 8 ), K[PhC(O)NP(S)Ph 2 ] ( 9 ), K[(C 5 H 4 N)C(S)NP(S)Ph 2 ] ( 10 ), and K[H 2 NC(S)NP(Se)Ph 2 ] ( 11 ). Reaction of 4 with KOBu and [Cu(Ph 3 P) 2 ][NO 3 ] gives [Cu(Ph 3 P)(PhC(O)NP(S)Ph 2 )] ( 12 ) which is the first crystallographically characterised example of a non‐ionic six‐membered “true” heterocycle (i.e. a ring in which every heterocatom is different). 9 and 10 were treated with [PdCl 2 (COD)] to give [Pd{PhC(O)NP(S)Ph 2 } 2 ] ( 13 ) and [Pd{(C 5 H 4 N)C(O)NP(S)Ph 2 } 2 ] ( 14 ), respectively The anion of 8 coordinates to zinc forming [Zn{H 2 NC(S)NP(S)Ph 2 } 2 ] ( 15 ). Treatment of 2 or 8 with [PtCl 2 (COD)] gives [Pt{H 2 NC(S)NP(S)Ph 2 }{H 2 NC(S)NHP(S)Ph 2 }] + Cl − ( 16 ) and [Pt{H 2 NC(S)NP(S)Ph 2 } 2 ] ( 17 ), respectively. The X‐ray structures of 12 , 15–17 are reported.