Shape-Selective Intercalation Reactions of Layered Zinc and Cobalt Phosphonates

Guang Cao, Thomas E. Mallouk

Research output: Contribution to journalArticle

181 Citations (Scopus)

Abstract

Dehydration of layered metal phosphonates M(O3PCH3)· H2O (M = Mg, Zn, Co) occurs topochemically to give anhydrous salts M(O3PCH3) with similar unit cell dimensions in the space group Pmn21 Mg(O3PCH3) absorbs water rapidly from air, forming Mg(O3PCH3)·H2O; Co(O3PCH3) does so less readily, and Zn(O3PCH3) is unreactive even with liquid water. Anhydrous Co and Zn salts M(O3PCH3) react with ammonia and primary amines to form intercalation compounds M(O3PCH3)(RNH2), R = H to n-C8H17. The intercalation reaction is shape-selective, as amines with branching at the α-carbon cannot access the metal coordination site. The packing of alkyl chains is different for primary amine intercalation compounds containing Co and Zn. In all Co(O3PCH3)(n-CnH2n+1NH2) compounds, the chains pack as double layers. In the Zn(O3PCH3)(n-C.,H2n+1NH2) series, compounds with even n also adopt double-layer structures, while odd n compounds form more efficiently packed interdigitated monolayers in the interlamellar region.

Original languageEnglish (US)
Pages (from-to)1434-1438
Number of pages5
JournalInorganic Chemistry
Volume30
Issue number7
DOIs
StatePublished - Apr 1 1991

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Organophosphonates
Intercalation
Cobalt
intercalation
Amines
Zinc
Intercalation compounds
amines
cobalt
zinc
Salts
Metals
salts
Water
Dehydration
Ammonia
dehydration
metals
water
ammonia

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Cao, Guang ; Mallouk, Thomas E. / Shape-Selective Intercalation Reactions of Layered Zinc and Cobalt Phosphonates. In: Inorganic Chemistry. 1991 ; Vol. 30, No. 7. pp. 1434-1438.
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Shape-Selective Intercalation Reactions of Layered Zinc and Cobalt Phosphonates. / Cao, Guang; Mallouk, Thomas E.

In: Inorganic Chemistry, Vol. 30, No. 7, 01.04.1991, p. 1434-1438.

Research output: Contribution to journalArticle

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N2 - Dehydration of layered metal phosphonates M(O3PCH3)· H2O (M = Mg, Zn, Co) occurs topochemically to give anhydrous salts M(O3PCH3) with similar unit cell dimensions in the space group Pmn21 Mg(O3PCH3) absorbs water rapidly from air, forming Mg(O3PCH3)·H2O; Co(O3PCH3) does so less readily, and Zn(O3PCH3) is unreactive even with liquid water. Anhydrous Co and Zn salts M(O3PCH3) react with ammonia and primary amines to form intercalation compounds M(O3PCH3)(RNH2), R = H to n-C8H17. The intercalation reaction is shape-selective, as amines with branching at the α-carbon cannot access the metal coordination site. The packing of alkyl chains is different for primary amine intercalation compounds containing Co and Zn. In all Co(O3PCH3)(n-CnH2n+1NH2) compounds, the chains pack as double layers. In the Zn(O3PCH3)(n-C.,H2n+1NH2) series, compounds with even n also adopt double-layer structures, while odd n compounds form more efficiently packed interdigitated monolayers in the interlamellar region.

AB - Dehydration of layered metal phosphonates M(O3PCH3)· H2O (M = Mg, Zn, Co) occurs topochemically to give anhydrous salts M(O3PCH3) with similar unit cell dimensions in the space group Pmn21 Mg(O3PCH3) absorbs water rapidly from air, forming Mg(O3PCH3)·H2O; Co(O3PCH3) does so less readily, and Zn(O3PCH3) is unreactive even with liquid water. Anhydrous Co and Zn salts M(O3PCH3) react with ammonia and primary amines to form intercalation compounds M(O3PCH3)(RNH2), R = H to n-C8H17. The intercalation reaction is shape-selective, as amines with branching at the α-carbon cannot access the metal coordination site. The packing of alkyl chains is different for primary amine intercalation compounds containing Co and Zn. In all Co(O3PCH3)(n-CnH2n+1NH2) compounds, the chains pack as double layers. In the Zn(O3PCH3)(n-C.,H2n+1NH2) series, compounds with even n also adopt double-layer structures, while odd n compounds form more efficiently packed interdigitated monolayers in the interlamellar region.

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