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  • PHYSICAL ORGANOMETALLIC CHEMISTRY VOLUME 3

    Unusual Structures and Physical Properties in Organometallic Chemistry Edited by

    MARCEL GIELEN Free University of Brussels, Belgium

    RUDOLPH WILLEM Free University of Brussels, Belgium

    BERND WRACKMEYER Universität Bayreuth, Germany

    Innodata 0470855614.jpg

  • Unusual Structures and Physical Properties in Organometallic Chemistry

  • Physical Organometallic Chemistry Editorial Board

    Marcel Gielen, Free University of Brussels, Belgium Rudolph Willem, Free University of Brussels, Belgium Bernd Wrackmeyer, Universität Bayreuth, Germany

    Books previously published in this Series

    Volume 1 Advanced Applications of NMR to Organometallic Chemistry

    Edited by Marcel Gielen, Free University of Brussels, Belgium Rudolph Willem, Free University of Brussels, Belgium Bernd Wrackmeyer, Universität Bayreuth, Germany ISBN 0 471 95938 3

    Volume 2 Solid State Organometallic Chemistry: Methods and Applications

    Edited by Marcel Gielen, Free University of Brussels, Belgium Rudolph Willem, Free University of Brussels, Belgium Bernd Wrackmeyer, Universität Bayreuth, Germany ISBN 0 471 97920 1

  • PHYSICAL ORGANOMETALLIC CHEMISTRY VOLUME 3

    Unusual Structures and Physical Properties in Organometallic Chemistry Edited by

    MARCEL GIELEN Free University of Brussels, Belgium

    RUDOLPH WILLEM Free University of Brussels, Belgium

    BERND WRACKMEYER Universität Bayreuth, Germany

  • Copyright 2002 John Wiley & Sons, Ltd, The Atrium West Sussex PO19 1UD, England

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  • Contents

    Contributors . . . . . . . . . . . . . . . . . . . . . . xv

    Series Preface . . . . . . . . . . . . . . . . . . . . . . xvii

    Preface . . . . . . . . . . . . . . . . . . . . . . . . xix

    1 Structure and Electrochemistry of Transition Metal Carbonyl Clusters with Interstitial or Semi-Interstitial Atoms: Contrast between Nitrides or Phosphides and Carbides Piero Zanello

    1 Introduction . . . . . . . . . . . . . . . . . . . . . 2 2 Homonuclear Clusters . . . . . . . . . . . . . . . . . 6

    2.1 Homonuclear Iron Clusters . . . . . . . . . . . . . . 6 2.1.1 Fe4(C)(CO)13 and [Fe4(C)(CO)12]

    2

    versus [Fe4(N)(CO)12] . . . . . . . . . . . . 6 2.1.2 Fe5(C)(CO)15 and [Fe5(C)(CO)14]

    2

    versus [Fe5(N)(CO)14] . . . . . . . . . . . . 11 2.1.3 [Fe6(C)(CO)16]

    2 versus [Fe6(N)(CO)15] 3 . . . . . 13

    2.2 Homonuclear Ruthenium Clusters . . . . . . . . . . . 15 2.2.1 Ru5(C)(CO)15 versus [Ru5(N)(CO)14] . . . . . . . 15 2.2.2 [Ru8(P)(CO)22] . . . . . . . . . . . . . . 15 2.2.3 [Ru10(C)(CO)24]

    2 . . . . . . . . . . . . . . 16 2.2.4 Further Structural Data . . . . . . . . . . . . 18

    2.3 Homonuclear Osmium Clusters . . . . . . . . . . . . 18 2.3.1 [Os5(C)(CO)14]

    2 and Os5(C)(CO)15. . . . . . . . 18 2.3.2 [Os6(P)(CO)18] . . . . . . . . . . . . . . . 18 2.3.3 [Os10(C)(CO)24]

    2 . . . . . . . . . . . . . . 19 2.3.4 Further Structural Data . . . . . . . . . . . . 20

    2.4 Homonuclear Cobalt Clusters . . . . . . . . . . . . . 21 2.4.1 [Co6(C)(CO)15]

    2 versus [Co6(N)(CO)15] and [Co6(P)(CO)16] ; [Co6(C)2(CO)18] . . . . . . . 21

    2.4.2 [Co7(N)(CO)15] 2 . . . . . . . . . . . . . . 22

    2.4.3 [Co8(C)(CO)18] 2 . . . . . . . . . . . . . . 24

    2.4.4 [Co9(P)(CO)21] 2 and [Co10(P)(CO)22]

    3 . . . . . . 24 2.4.5 [(Co13(C)2(CO)24]

    4 versus [Co13(N)2(CO)24] 3 . . . . 24

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  • 2.4.6 Further Structural Data . . . . . . . . . . . . 27 2.5 Homonuclear Rhodium Clusters . . . . . . . . . . . . 29

    2.5.1 [Rh6(C)(CO)15] 2 versus [Rh6(N)(CO)15] . . . . . 29

    2.5.2 [Rh7(N)(CO)15] 2 . . . . . . . . . . . . . . 30

    2.5.3 [Rh12(C)2(CO)24] 2 . . . . . . . . . . . . . 30

    2.5.4 Further Structural Data . . . . . . . . . . . . 31 2.6 Homonuclear Nickel Clusters . . . . . . . . . . . . . 32

    2.6.1 [Ni9(C)(CO)17] 2 . . . . . . . . . . . . . . 32

    2.6.2 [Ni32(C)6(CO)36] 6 . . . . . . . . . . . . . . 32

    2.6.3 [Ni38(C)6(CO)42] 6 . . . . . . . . . . . . . . 34

    2.6.4 Further Structural Data . . . . . . . . . . . . 34 2.7 Homonuclear Rhenium Clusters . . . . . . . . . . . . 35

    2.7.1 [Re7(C)(CO)21] 3 and [Re8(C)(CO)24]

    2 . . . . . . 35 2.7.2 Further Structural Data . . . . . . . . . . . . 36

    3 Heteronuclear Clusters . . . . . . . . . . . . . . . . . 36 3.1 Heteronuclear Iron Clusters . . . . . . . . . . . . . . 36

    3.1.1 Heteronuclear Iron–Molybdenum Clusters . . . . . 36 3.1.2 Heteronuclear Iron–Ruthenium Clusters . . . . . . 36 3.1.3 Heteronuclear Iron–Rhodium Clusters . . . . . . 36

    3.1.3.1 [Fe5Rh(N)(CO)15] 2 and

    [Fe4Rh2(N)(CO)15] . . . . . . . . . . 36 3.1.3.2 Further Structural Data. . . . . . . . . 36

    3.1.4 Heteronuclear Iron–Iridium Clusters . . . . . . . 38 3.1.5 Heteronuclear Iron–Nickel clusters . . . . . . . . 38

    3.1.5.1 [Fe6Ni6(N)2(CO)24] 2 . . . . . . . . . 38

    3.1.6 Heteronuclear Iron–Platinum Clusters . . . . . . . 39 3.1.7 Heteronuclear Iron–Mercury Clusters . . . . . . . 39

    3.1.7.1 {µ4-Hg[Fe5(C)(CO)14]2} 2 . . . . . . . . 39

    3.2 Heteronuclear Ruthenium Clusters . . . . . . . . . . . 40 3.2.1 Heteronuclear Ruthenium–Platinum Clusters . . . . 40 3.2.2 Heteronuclear Ruthenium–Mercury Clusters . . . . 40

    3.3 Heteronuclear Osmium Clusters . . . . . . . . . . . . 40 3.3.1 Heteronuclear Osmium–Mercury Clusters:

    [Os18Hg3(C)2(CO)42] 2 , [Os18Hg2(C)2(CO)42]

    4

    and [Os18Hg2(C)2(CO)42] 2 . . . . . . . . . . . 40

    3.4 Heteronuclear Cobalt Clusters . . . . . . . . . . . . . 41 3.4.1 Heteronuclear Cobalt–Nickel Clusters:

    [Co2Ni10(C)(CO)20] 2 , [Co3Ni9(C)(CO)20]

    2 and [Co6Ni2(C)2(CO)16]

    2 . . . . . . . . . . . . . 41 3.5 Heteronuclear Rhodium Clusters . . . . . . . . . . . . 44

    3.5.1 Heteronuclear Rhodium–Platinum Clusters . . . . . 44 3.5.2 Heteronuclear Rhodium–Cobalt Clusters. . . . . . 45 3.5.3 Heteronuclear Rhodium–Iridium Clusters . . . . . 45 3.5.4 Heteronuclear Rhodium–Silver Clusters . . . . . . 45

    vi CONTENTS

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  • 4 Acknowledgements . . . . . . . . . . . . . . . . . . 45 5 References . . . . . . . . . . . . . . . . . . . . . 45

    2 Unusual Nuclear Magnetic Shielding and Coupling Constants Related to Unusual Bonding Situations Bernd Wrackmeyer

    1 Introduction . . . . . . . . . . . . . . . . . . . . . 51 1.1 General . . . . . . . . . . . . . . . . . . . . . 51 1.2 Chemical Shifts, δX . . . . . . . . . . . . . . . . . 54 1.3 Coupling Constants, nJ(A, X) . . . . . . . . . . . . . 57

    2 Hydrides . . . . . . . . . . . . . . . . . . . . . . 58 2.1 Boron Hydrides . . . . . . . . . . . . . . . . . . 58 2.2 Unusual Chemical Shifts, δ1H, of Hydrocarbons . . . . . . 59 2.3 Carbocations . . . . . . . . . . . . . . . . . . . 60 2.4 Hydrogen Bonding Involving Nitrogen, Oxygen and

    Fluorine . . . . . . . . . . . . . . . . . . . . . 60 2.5 Transiti

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