TY - JOUR
T1 - Azamacrocyclic stabilisation of the halogenocations MX3+ where M = Ge or Sn and X = Cl or Br. Synthesis and molecular structures of [GeCl3(L1)]+2[H3O] +Cl-3·MeCN, [SnCl3(L1)]+2[SnCl6] 2-·4MeCN ...
AU - Willey, Gerald R.
AU - Woodman, Timothy J.
AU - Somasundaram, Usha
AU - Aris, Damian R.
AU - Errington, William
PY - 1998/8/7
Y1 - 1998/8/7
N2 - Title full: Azamacrocyclic stabilisation of the halogenocations MX3+ where M = Ge or Sn and X = Cl or Br. Synthesis and molecular structures of [GeCl3(L1)]+2[H3O] +Cl-3·MeCN, [SnCl3(L1)]+2[SnCl6] 2-·4MeCN, [GeBr3(L2)]+2[MeNH3] +Br-3·MeCN and [SnBr3(L2)]+2[SnBr6] 2- where L1 = 1,4,7-trimethyl-1,4,7-triazacyclononane and L2 = 1,3,5-trimethyl-1,3,5-triazacyclohexane. Treatment (1 : 1 in acetonitrile) of the reaction systems MCl4-1,4,7-trimethyl-1,4,7-triazacyclononane (L1) and MBr4-1,3,5-trimethyl-1,3,5-triazacyclohexane (L2), where MIV = Ge or Sn, provided ionic compounds featuring the trihalogenocationic species [MX3(Ln)]+ rather than direct adduct formation [MX4(Ln)]. Crystal structure determinations (X-ray diffraction) confirmed an ionic formulation for each of the four products isolated, viz. [GeCl3(L1)]+2[H3O] +Cl-3·MeCN 1, [SnCl3(L1)]+2[Sncl6] 2-·4MeCN 2, [GeBr3(L2)]+2[MeNH3] +Br-3·MeCN 3, and [SnBr3(L2)]+2[SnBr6] 2- 4. Ligand attachment to MIV, both for L1 and L2, is terdentate N-donor (η3) throughout and the resulting six-co-ordinate cations [MX3(Ln)]+ show the anticipated fac-octahedral metal geometry. Individual M-N bond distances within each cation are the same, viz. mean values 2.113(2) 1, 2.244(8) 2, 2.142(7) 3, 2.311(6) Å 4, reflecting a uniform central location of the MX3+ unit over the ring cavity. The 'cone angle' Nring-M-Nring values (mean) for compounds 3 64.3(3) and 4 59.7(2)° involving L2 are conspicuously smaller, ca. 20°, than those for compounds 1 82.90(8) and 2 79.1(3)° involving L1 as a reflection of the insistent steric demands of the more compact six-membered triazacyclohexane ligand.
AB - Title full: Azamacrocyclic stabilisation of the halogenocations MX3+ where M = Ge or Sn and X = Cl or Br. Synthesis and molecular structures of [GeCl3(L1)]+2[H3O] +Cl-3·MeCN, [SnCl3(L1)]+2[SnCl6] 2-·4MeCN, [GeBr3(L2)]+2[MeNH3] +Br-3·MeCN and [SnBr3(L2)]+2[SnBr6] 2- where L1 = 1,4,7-trimethyl-1,4,7-triazacyclononane and L2 = 1,3,5-trimethyl-1,3,5-triazacyclohexane. Treatment (1 : 1 in acetonitrile) of the reaction systems MCl4-1,4,7-trimethyl-1,4,7-triazacyclononane (L1) and MBr4-1,3,5-trimethyl-1,3,5-triazacyclohexane (L2), where MIV = Ge or Sn, provided ionic compounds featuring the trihalogenocationic species [MX3(Ln)]+ rather than direct adduct formation [MX4(Ln)]. Crystal structure determinations (X-ray diffraction) confirmed an ionic formulation for each of the four products isolated, viz. [GeCl3(L1)]+2[H3O] +Cl-3·MeCN 1, [SnCl3(L1)]+2[Sncl6] 2-·4MeCN 2, [GeBr3(L2)]+2[MeNH3] +Br-3·MeCN 3, and [SnBr3(L2)]+2[SnBr6] 2- 4. Ligand attachment to MIV, both for L1 and L2, is terdentate N-donor (η3) throughout and the resulting six-co-ordinate cations [MX3(Ln)]+ show the anticipated fac-octahedral metal geometry. Individual M-N bond distances within each cation are the same, viz. mean values 2.113(2) 1, 2.244(8) 2, 2.142(7) 3, 2.311(6) Å 4, reflecting a uniform central location of the MX3+ unit over the ring cavity. The 'cone angle' Nring-M-Nring values (mean) for compounds 3 64.3(3) and 4 59.7(2)° involving L2 are conspicuously smaller, ca. 20°, than those for compounds 1 82.90(8) and 2 79.1(3)° involving L1 as a reflection of the insistent steric demands of the more compact six-membered triazacyclohexane ligand.
UR - http://www.scopus.com/inward/record.url?scp=36849054687&partnerID=8YFLogxK
U2 - 10.1039/a803175d
DO - 10.1039/a803175d
M3 - Article
AN - SCOPUS:36849054687
SN - 0300-9246
SP - 2573
EP - 2576
JO - Journal of the Chemical Society - Dalton Transactions
JF - Journal of the Chemical Society - Dalton Transactions
IS - 15
ER -