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La 2 MgNi 2 H 8 , the first mixed polyanionic transition metal hydride. J-N. Chotard, Y. Filinchuk, K. Yvon. SSCr Meeting, Bern, 2006. J-N. Chotard, Y. Filinchuk, K. Yvon. Introduction. Complex metal hydrides

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slide1

La2MgNi2H8, the first mixed polyanionic transition metal hydride

J-N. Chotard, Y. Filinchuk, K. Yvon

SSCr Meeting, Bern, 2006

J-N. Chotard, Y. Filinchuk, K. Yvon

slide2

Introduction

Complex metal hydrides

~ 80 compounds containing ~ 30 different transition metal hydride complexes:almost all of them are mononuclear

1st polynuclear hydride complexes based on 3d-metal

[Ni2H7]7- & [Ni4H12]12-

SSCr Meeting, Bern, 2006

J-N. Chotard, Y. Filinchuk, K. Yvon

slide3

Synthesis and structure determ.

  • La2MgNi2: arc-melting La and Ni, sintering the product with Mg
  • La2MgNi2H8: hydrogenation/deuteration in an autoclave:30 bar, 100°C

High-resolution synchrotron powder diffraction (SNBL at ESRF):indexing, metal structure (FOX), Rietveld

High-resolution neutron powder diffraction (HRPT, SINQ, PSI):16 deuterium atom positions (FOX), Rietveld

SSCr Meeting, Bern, 2006

J-N. Chotard, Y. Filinchuk, K. Yvon

slide4

Structure of La2MgNi2H8

Metal atom shifts < 0.65 Å

La2MgNi2

La2MgNi2H8

Tetragonal Monoclinic

7.64

3.94 Å

11.84

7.82

11.96 Å

92.78 °

SSCr Meeting, Bern, 2006

J-N. Chotard, Y. Filinchuk, K. Yvon

slide5

Two types of D-atom positions

La2MgNi2

La2MgNi2H8

SSCr Meeting, Bern, 2006

J-N. Chotard, Y. Filinchuk, K. Yvon

slide6

Bonding :18 electron rule

La3+, Mg2+[Ni2H7]7-, [Ni4H12]12-, H-

64 electrons

34 electrons

This concept is supported by observed changes in physical properties

SSCr Meeting, Bern, 2006

J-N. Chotard, Y. Filinchuk, K. Yvon

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