Complexes of group 1 salts with N,N′-aromatic bidentate ligands, of 1:1 salt: Base ratio

Jarrod H.N. Buttery; Effendy; Siti Mutrofin; Neil C. Plackett; Brian W. Skelton; Claire R. Whitaker; Allan H. White

doi:10.1002/zaac.200600079

Complexes of group 1 salts with N,N′-aromatic bidentate ligands, of 1:1 salt: Base ratio

Jarrod H.N. Buttery^*
, Effendy
, Siti Mutrofin
, Neil C. Plackett
, Brian W. Skelton
, Claire R. Whitaker
, Allan H. White

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

23 Citations (Scopus)

Abstract

The present and three subsequent papers describe the syntheses and structural characterization of crystalline adducts, sometimes solvated, obtained from (usually methanolic) solutions of simple group 1 metal salts, MX, with the N,N′-aromatic bases L = 2,2′-bipyridine ('bpy'), 1,10-phenanthroline ('phen') and 2,9-dimethyl,1,10-phenanthroline ('dmp') of 1:n (n = 1,2,3 and some non-integral) stoichiometries and anhydrous conditions. X are predominantly weakly basic oxyanions ClO₄, NO₃, O ₃SCF₃ (= 'triflate', 'tfs') and (pseudo-) halides for M = Li, Na, K, Rb (not, as yet, 'tfs'). The present paper describes adducts of 1:1 (or near 1:1) MX : L stoichiometry. The majority of arrays described are single-stranded one-dimensional linear polymers, LM units being bridged by oxyanions: single-stranded LiNO₃: dmp (1:1) _(∞|∞), (the Na analogue is isomorphous, but with a different anion bonding mode), and double-stranded NaClO₄: bpy (1:1)_(∞|∞) and Mtfs: dmp (1:1)(∞|∞) (M = Na, K, Rb): an interesting single-stranded 'hydrolysis' product, with supernumerary interleaving phen moieties 'solvating' as well as methanol, is defined as NaI: phen: H₂O: MeOH (1:1(+1):2:1), [(phen)Na(μ-OH₂) ₂]_(∞|∞)I·phen·MeOH. The complex LiCl : dmp (2:2) is a dimer, [(dmp)Li(μ-Cl)₂Li(dmp)], while the LiBr : dmp system is defined in terms of two ionic adductsLiBr : dmp : MeOH (1:1:2.5) = [(dmp)Li(HOMe)₂]Br· 0.5MeOH and LiBr : dmp : MeOH : H₂O (1:1(+1):1:1), 'solvated' with dmp, MeOH and H₂O, as [(dmp)Li(HOMe)(OH₂)]Br-dmp; also of this family is LiNCS : dmp : MeOH (1:1:1) ≡ [(dmp)Li(yVCS)(HOMe)]. The adduct KPF₆ : dmp (1:1)_(∞|∞), is a novel double-stranded one-dimensional polymer in which (dmp)K units are bridged by PF₆ counterions. Ktfs : dmp : MeOH (2:2:1)₂ is a complex tetramer in which all species are coordinated, but its rubidium counterpart is an infinite polymer. Of more complex stoichiometry are the adducts KI : dmp : MeOH (6:8:3) = [K ₆I₄(dmp)₈]I₂·3MeOH containing a 'polyiodide' cation, and Ktfs : dmp (4:3), a double-stranded, one-dimensional polymer.

Original language	English
Pages (from-to)	1809-1828
Number of pages	20
Journal	Zeitschrift fur Anorganische und Allgemeine Chemie
Volume	632
Issue number	10-11
DOIs	https://doi.org/10.1002/zaac.200600079
Publication status	Published - 2006
Externally published	Yes

Keywords

Group 1 complexes
N,N′-bidentate ligand complexes
X-Ray crystal structures

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10.1002/zaac.200600079

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@article{9c65df0490034c2fb8da3e37f8812a1c,

title = "Complexes of group 1 salts with N,N′-aromatic bidentate ligands, of 1:1 salt: Base ratio",

abstract = "The present and three subsequent papers describe the syntheses and structural characterization of crystalline adducts, sometimes solvated, obtained from (usually methanolic) solutions of simple group 1 metal salts, MX, with the N,N′-aromatic bases L = 2,2′-bipyridine ('bpy'), 1,10-phenanthroline ('phen') and 2,9-dimethyl,1,10-phenanthroline ('dmp') of 1:n (n = 1,2,3 and some non-integral) stoichiometries and anhydrous conditions. X are predominantly weakly basic oxyanions ClO4, NO3, O 3SCF3 (= 'triflate', 'tfs') and (pseudo-) halides for M = Li, Na, K, Rb (not, as yet, 'tfs'). The present paper describes adducts of 1:1 (or near 1:1) MX : L stoichiometry. The majority of arrays described are single-stranded one-dimensional linear polymers, LM units being bridged by oxyanions: single-stranded LiNO3: dmp (1:1) (∞|∞), (the Na analogue is isomorphous, but with a different anion bonding mode), and double-stranded NaClO4: bpy (1:1)(∞|∞) and Mtfs: dmp (1:1)(∞|∞) (M = Na, K, Rb): an interesting single-stranded 'hydrolysis' product, with supernumerary interleaving phen moieties 'solvating' as well as methanol, is defined as NaI: phen: H2O: MeOH (1:1(+1):2:1), [(phen)Na(μ-OH2) 2](∞|∞)I·phen·MeOH. The complex LiCl : dmp (2:2) is a dimer, [(dmp)Li(μ-Cl)2Li(dmp)], while the LiBr : dmp system is defined in terms of two ionic adductsLiBr : dmp : MeOH (1:1:2.5) = [(dmp)Li(HOMe)2]Br· 0.5MeOH and LiBr : dmp : MeOH : H2O (1:1(+1):1:1), 'solvated' with dmp, MeOH and H2O, as [(dmp)Li(HOMe)(OH2)]Br-dmp; also of this family is LiNCS : dmp : MeOH (1:1:1) ≡ [(dmp)Li(yVCS)(HOMe)]. The adduct KPF6 : dmp (1:1)(∞|∞), is a novel double-stranded one-dimensional polymer in which (dmp)K units are bridged by PF6 counterions. Ktfs : dmp : MeOH (2:2:1)2 is a complex tetramer in which all species are coordinated, but its rubidium counterpart is an infinite polymer. Of more complex stoichiometry are the adducts KI : dmp : MeOH (6:8:3) = [K 6I4(dmp)8]I2·3MeOH containing a 'polyiodide' cation, and Ktfs : dmp (4:3), a double-stranded, one-dimensional polymer.",

keywords = "Group 1 complexes, N,N′-bidentate ligand complexes, X-Ray crystal structures",

author = "Buttery, \{Jarrod H.N.\} and Effendy and Siti Mutrofin and Plackett, \{Neil C.\} and Skelton, \{Brian W.\} and Whitaker, \{Claire R.\} and White, \{Allan H.\}",

year = "2006",

doi = "10.1002/zaac.200600079",

language = "English",

volume = "632",

pages = "1809--1828",

journal = "Zeitschrift fur Anorganische und Allgemeine Chemie",

issn = "0044-2313",

publisher = "Wiley-VCH Verlag",

number = "10-11",

}

TY - JOUR

T1 - Complexes of group 1 salts with N,N′-aromatic bidentate ligands, of 1:1 salt

T2 - Base ratio

AU - Buttery, Jarrod H.N.

AU - Effendy,

AU - Mutrofin, Siti

AU - Plackett, Neil C.

AU - Skelton, Brian W.

AU - Whitaker, Claire R.

AU - White, Allan H.

PY - 2006

Y1 - 2006

N2 - The present and three subsequent papers describe the syntheses and structural characterization of crystalline adducts, sometimes solvated, obtained from (usually methanolic) solutions of simple group 1 metal salts, MX, with the N,N′-aromatic bases L = 2,2′-bipyridine ('bpy'), 1,10-phenanthroline ('phen') and 2,9-dimethyl,1,10-phenanthroline ('dmp') of 1:n (n = 1,2,3 and some non-integral) stoichiometries and anhydrous conditions. X are predominantly weakly basic oxyanions ClO4, NO3, O 3SCF3 (= 'triflate', 'tfs') and (pseudo-) halides for M = Li, Na, K, Rb (not, as yet, 'tfs'). The present paper describes adducts of 1:1 (or near 1:1) MX : L stoichiometry. The majority of arrays described are single-stranded one-dimensional linear polymers, LM units being bridged by oxyanions: single-stranded LiNO3: dmp (1:1) (∞|∞), (the Na analogue is isomorphous, but with a different anion bonding mode), and double-stranded NaClO4: bpy (1:1)(∞|∞) and Mtfs: dmp (1:1)(∞|∞) (M = Na, K, Rb): an interesting single-stranded 'hydrolysis' product, with supernumerary interleaving phen moieties 'solvating' as well as methanol, is defined as NaI: phen: H2O: MeOH (1:1(+1):2:1), [(phen)Na(μ-OH2) 2](∞|∞)I·phen·MeOH. The complex LiCl : dmp (2:2) is a dimer, [(dmp)Li(μ-Cl)2Li(dmp)], while the LiBr : dmp system is defined in terms of two ionic adductsLiBr : dmp : MeOH (1:1:2.5) = [(dmp)Li(HOMe)2]Br· 0.5MeOH and LiBr : dmp : MeOH : H2O (1:1(+1):1:1), 'solvated' with dmp, MeOH and H2O, as [(dmp)Li(HOMe)(OH2)]Br-dmp; also of this family is LiNCS : dmp : MeOH (1:1:1) ≡ [(dmp)Li(yVCS)(HOMe)]. The adduct KPF6 : dmp (1:1)(∞|∞), is a novel double-stranded one-dimensional polymer in which (dmp)K units are bridged by PF6 counterions. Ktfs : dmp : MeOH (2:2:1)2 is a complex tetramer in which all species are coordinated, but its rubidium counterpart is an infinite polymer. Of more complex stoichiometry are the adducts KI : dmp : MeOH (6:8:3) = [K 6I4(dmp)8]I2·3MeOH containing a 'polyiodide' cation, and Ktfs : dmp (4:3), a double-stranded, one-dimensional polymer.

AB - The present and three subsequent papers describe the syntheses and structural characterization of crystalline adducts, sometimes solvated, obtained from (usually methanolic) solutions of simple group 1 metal salts, MX, with the N,N′-aromatic bases L = 2,2′-bipyridine ('bpy'), 1,10-phenanthroline ('phen') and 2,9-dimethyl,1,10-phenanthroline ('dmp') of 1:n (n = 1,2,3 and some non-integral) stoichiometries and anhydrous conditions. X are predominantly weakly basic oxyanions ClO4, NO3, O 3SCF3 (= 'triflate', 'tfs') and (pseudo-) halides for M = Li, Na, K, Rb (not, as yet, 'tfs'). The present paper describes adducts of 1:1 (or near 1:1) MX : L stoichiometry. The majority of arrays described are single-stranded one-dimensional linear polymers, LM units being bridged by oxyanions: single-stranded LiNO3: dmp (1:1) (∞|∞), (the Na analogue is isomorphous, but with a different anion bonding mode), and double-stranded NaClO4: bpy (1:1)(∞|∞) and Mtfs: dmp (1:1)(∞|∞) (M = Na, K, Rb): an interesting single-stranded 'hydrolysis' product, with supernumerary interleaving phen moieties 'solvating' as well as methanol, is defined as NaI: phen: H2O: MeOH (1:1(+1):2:1), [(phen)Na(μ-OH2) 2](∞|∞)I·phen·MeOH. The complex LiCl : dmp (2:2) is a dimer, [(dmp)Li(μ-Cl)2Li(dmp)], while the LiBr : dmp system is defined in terms of two ionic adductsLiBr : dmp : MeOH (1:1:2.5) = [(dmp)Li(HOMe)2]Br· 0.5MeOH and LiBr : dmp : MeOH : H2O (1:1(+1):1:1), 'solvated' with dmp, MeOH and H2O, as [(dmp)Li(HOMe)(OH2)]Br-dmp; also of this family is LiNCS : dmp : MeOH (1:1:1) ≡ [(dmp)Li(yVCS)(HOMe)]. The adduct KPF6 : dmp (1:1)(∞|∞), is a novel double-stranded one-dimensional polymer in which (dmp)K units are bridged by PF6 counterions. Ktfs : dmp : MeOH (2:2:1)2 is a complex tetramer in which all species are coordinated, but its rubidium counterpart is an infinite polymer. Of more complex stoichiometry are the adducts KI : dmp : MeOH (6:8:3) = [K 6I4(dmp)8]I2·3MeOH containing a 'polyiodide' cation, and Ktfs : dmp (4:3), a double-stranded, one-dimensional polymer.

KW - Group 1 complexes

KW - N,N′-bidentate ligand complexes

KW - X-Ray crystal structures

UR - https://www.scopus.com/pages/publications/33748427622

U2 - 10.1002/zaac.200600079

DO - 10.1002/zaac.200600079

M3 - Article

AN - SCOPUS:33748427622

SN - 0044-2313

VL - 632

SP - 1809

EP - 1828

JO - Zeitschrift fur Anorganische und Allgemeine Chemie

JF - Zeitschrift fur Anorganische und Allgemeine Chemie

IS - 10-11

ER -

Complexes of group 1 salts with N,N′-aromatic bidentate ligands, of 1:1 salt: Base ratio

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Keywords

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