Cover Page

Board of Directors

GREGORY S. GIROLAMI, President University of Illinois at Urbana‐Champaign
ALFRED P. SATTELBERGER, Treasurer Argonne National Laboratory
STOSH A. KOZIMOR Los Alamos National Laboratory
PHILIP P. POWER University of California at Davis
THOMAS B. RAUCHFUSS University of Illinois at Urbana‐Champaign
CHRISTINE M. THOMAS Brandeis University


Secretary to the Corporation

STANTON S. CHING Connecticut College


Future Volumes

38 TBA

Editor‐in‐Chief

PHILIP P. POWER

University of California at Davis

INORGANIC SYNTHESES

Volume 37







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DEDICATION

This volume is dedicated to the memory of Donald C. Bradley, Malcolm H. Chisholm, Michael F. Lappert, and Sheldon G. Shore, four giants in synthetic inorganic chemistry.

PHILIP P. POWER

University of California, Davis, CA

NOTE TO CONTRIBUTORS AND CHECKERS

The Inorganic Syntheses series (www.inorgsynth.com) publishes detailed and independently checked procedures for making important inorganic and organometallic compounds. Thus, the series is the concern of the entire scientific community. The Editorial Board hopes that many chemists will share in the responsibility of producing Inorganic Syntheses by offering their advice and assistance in both the formulation and the laboratory evaluation of outstanding syntheses.

The major criterion by which syntheses are judged is their potential value to the scientific community. We hope that the syntheses will be widely used and provide access to a broad range of compounds of importance in current research. The syntheses represent the best available procedures, and new or improved syntheses of well‐established compounds are often featured. Syntheses of compounds that are available commercially at reasonable prices are ordinarily not included, however, unless the procedure illustrates some useful technique. Inorganic Syntheses is not a repository of primary research data, and therefore submitted syntheses should have already appeared in some form in the primary peer‐reviewed literature and, at least to some extent, passed the “test of time.” The series offers authors the chance to describe the intricacies of synthesis and purification in greater detail than possible in the original literature, as well as to provide updates of an established synthesis.

Authors wishing to submit syntheses for possible publication should write their manuscripts in a style that conforms with that of previous volumes of Inorganic Syntheses (a style guide is available from the Board Secretary). The manuscript should be in English and submitted as an editable electronic document. Nomenclature should be consistent and should follow the recommendations presented in Nomenclature of Inorganic Chemistry, IUPAC Recommendations 2005, published for the International Union of Pure and Applied Chemistry by the Royal Society of Chemistry, Cambridge, 2005. This document is available online (as of 2012) at http://www.iupac.org/fileadmin/user_upload/databases/Red_Book_2005.pdf. Abbreviations should conform to those used in publications of the American Chemical Society, particularly Inorganic Chemistry.

Submissions should consist of four sections: Introduction, Procedure, Properties, and References. The Introduction should include an indication of the importance and utility of the product(s) in question and a concise and critical summary of the available procedures for making them and what advantage(s) the chosen method has over the alternatives. The Procedure should present detailed and unambiguous laboratory directions and be written so that it anticipates possible mistakes and misunderstandings on the part of the person who attempts to duplicate the procedure. It should contain an admonition if any potential hazards are associated with the procedure and what safety precautions should be taken. Sources of unusual starting materials must be given, and, if possible, minimal standards of purity of reagents and solvents should be stated. Ideally, all reagents are readily available commercially or have been described in earlier volumes of Inorganic Syntheses. The scale should be reasonable for normal laboratory operation, and problems involved in scaling the procedure either up or down should be discussed if known. Unusual equipment or procedures should be clearly described and, if necessary for clarity, illustrated in line drawings. The yield should be given both in mass and in percentage based on theory. The Procedure section normally will conclude with calculated and found microanalytical data. The Properties section should supply and discuss those physical and chemical characteristics that are relevant to judging the purity of the product and to permitting its handling and use in an intelligent manner. Under References, pertinent literature citations should be listed in the order they appear in the text.

Manuscripts should be submitted electronically to the Secretary of the Editorial Board, Professor Stanton Ching (sschi@conncoll.edu). The Editorial Board determines whether submitted syntheses meet the general specifications outlined above. Every procedure will be checked in an independent laboratory, and publication is contingent on satisfactory duplication of the syntheses. For online access to information and requirements, see www.inorgsynth.com.

Chemists willing to check syntheses should contact the editor of a future volume or make this information known to Professor Ching.

Volume 36 included two different preparations of tungsten oxotetrachloride, WOCl4. These preparations were originally described in the following two papers, which should have been cited: H.‐J. Lunk and W. Petke, Z. Chem. 14, 365 (1974) and V. C. Gibson, T. P. Kee, and A. Shaw, Polyhedron 7, 579 (1988). In addition, because the tungsten content of WOCl4 samples is less sensitive to the presence of impurities, it is best to assess purity by means of a chloride microanalysis: Calcd. Cl, 41.5%. We thank Dr. Lunk for bringing this information to our attention.

TOXIC SUBSTANCES AND LABORATORY HAZARDS

Chemicals and chemistry are by their very nature hazardous. All reasonable care should be taken to avoid inhalation or other physical contact with reagents and solvents used in this volume. In addition, particular attention should be paid to avoiding sparks, open flames, or other potential sources that could set fire to combustible vapors or gases. The specific hazards in the syntheses reported in this volume are delineated, where appropriate, in the experimental procedure. It is impossible, however, to foresee every eventuality, such as a new biological effect of a common laboratory reagent. As a consequence, all chemicals used and all reactions described in this volume should be viewed as potentially hazardous.

The following sources are recommended for guidance:

  • NIOSH Pocket Guide to Chemical Hazards, US Government Printing Office, Washington, DC, 2005 (ISBN‐13: 978‐1‐59804‐052‐4), is available free at http://www.cdc.gov/niosh/npg/and can be purchased in paperback and spiral bound format. It contains information and data for 677 common compounds and classes of compounds.
  • Organic Syntheses, which is available online at http://www.orgsyn.org, has a concise but useful section “Handling Hazardous Chemicals.”
  • Prudent Practices in the Laboratory: Handling and Disposal of Chemicals, National Academy Press, 1995 (ISBN‐13: 978‐0‐30905‐229‐0), is available free at http://www.nap.edu/catalog.php?record_id=4911.
  • Amarego, W.L.F. and Chai, C. (2009). Purification of Laboratory Chemicals, 6e. Oxford: Butterworth‐Heinemann, (ISBN‐13: 978‐1‐85617‐567‐8), is the standard reference for the purification of reagents and solvents. Special attention should be paid to the purification and storage of ethers.

PREFACE

This volume of Inorganic Syntheses presents detailed descriptions of the synthesis of more than one hundred compounds drawn from the main group and transition metal elements. More than half of the compounds have been chosen mainly for their synthetic utility, that is to say, they can serve as synthons by simple procedures for a wide range of other compounds. The bis(trimethylsilyl)amido derivatives of manganese, iron, cobalt, or the group 2 or 14 elements are prominent examples of such synthons. In addition, these amides are inexpensive and relatively easily prepared. Furthermore, they are highly useful hydrocarbon‐soluble sources of their masked divalent metal ions.

A further prominent theme in this volume is the synthesis of sterically crowding ligands that have enabled the isolation of species with unusual coordination numbers and multiple bonding. These are exemplified by the terphenyl ligands, which feature a central aryl ring bound to two flanking aryl rings at the ortho positions. The latter rings are further substituted by alkyl groups, thus creating a sterically protected area around the element to which the terphenyl is attached. These terphenyl ligands also bear a steric resemblance to β‐diketiminate or Nacnac ligands that carry aryl groups at their nitrogen atoms and were the subject of a large chapter (Chapter 1) of Volume 35 of Inorganic Syntheses.

A noteworthy inclusion in this volume is the syntheses of species having the first stable well‐characterized examples of magnesium–magnesium and zinc─zinc bonds. These provide a striking illustration of how compounds of a completely new class with unprecedented bonding can be synthesized by relatively straightforward routes using readily accessible ligands, i.e. the abovementioned β‐diketiminate and the well‐known pentamethylcyclopentadienyl ligands.

This volume is organized into eight chapters. Some background and historical perspective are provided in the introduction to each chapter. The opening chapter describes the synthesis and characterization data for the above‐mentioned divalent transition metal silylamides [M{N(SiMe3)2}2]2 (M = Mn, Fe, and Co) and their tetrahydrofuran complexes. The silylamide theme is continued in Chapter 2, where the synthesis of the group 2 compounds [M{N(SiMe3)2}2]2 (M = Ca and Sr) and the monomeric group 14 derivatives M{N(SiMe3)2}2 (M = Ge, Sn, or Pb) are detailed. In addition, the synthesis of some 2,2,6,6‐tetramethylpiperidido and N(Pri) anilido salts of potassium or calcium are described.

The preparations of the abovementioned groundbreaking metal–metal bonded (η5‐C5Me5)ZnZn(η5‐C5Me5) and NacnacMgMgNacnac complexes are the subject of Chapter 3. Chapter 4 features the synthesis of several sterically crowded main group and transition metal organometallic complexes. These include the simple dimeric, divalent diaryl (FeMes2)2 (Mes = C6H2‐2,4,6‐Me3), and the monomeric bisterphenyl derivatives M(C6H3‐2,6‐Mes2)2 (M = Mn, Fe, and Co). Included also are the syntheses of the precursor iodo and lithium derivatives. Similarly, the bent, highly colored group 14 element congeners M(C6H3‐2,6‐Mes2)2 (M = Ge, Sn, or Pb) are delineated. In addition, the synthesis of the related terphenyl gallium species as well as η4‐bonded bisanthracene anionic complexes of iron and cobalt is given.

In Chapter 5, the syntheses of 20 sterically crowded terphenyl compounds are detailed. These include preparations featuring the terphenyl groups ─C6H3‐2,6‐Mes2, ─C6H3‐2,6‐Dipp2 (Dipp = 2,6‐di‐iso‐propylphenyl), and ─C6H3‐2,6‐Trip2 (Trip = 2,4,6‐tri‐iso‐propylphenyl), which include the preparations of their iodo precursors, their lithium salts, azide, aniline, phenol, thiol, and isocyanide derivatives. These derivatives have proven extremely useful in supporting an extensive chemistry of compounds from the s, p, d, and f blocks of the periodic table.

In Chapter 6, the isolation of white phosphorus from red phosphorus is given by two methods involving the thermolysis of commercially available red phosphorus. In addition, the synthesis of the unusual species AsP3 from a niobium triphosphide and arsenic trihalide is described. Chapter 7 focuses on the synthesis of various unusual group 13 element derivatives. The synthesis of the pioneering aluminum(I) compound {Al(η5‐C5Me5)}4 by two approaches is described, as is that of the unusual Al(C6F5)3∙toluene complex. In addition, the synthesis of various organometallic group 13–15 compounds of relevance to materials chemistry is given.

The final chapter describes the synthesis of a variety of compounds – mainly derivatives of transition metals – that do not fit conveniently into the themes of the earlier chapters. Examples include the (1R,2R‐diaminocyclohexane)oxalatoplatinum(II) or oxaliplatin, which is marketed as the colorectal anticancer drug Eloxatin, the palladium complex tris(dibenzylideneacetone)dipalladium(II), and a series of gold(I) and (II) amidinate complexes. In addition, there are syntheses of chromium(III) acetonitrile complexes, as well as a series of ruthenium dimethylsulfoxide derivatives. From the early transition metal groups, there are the titanium(III) amide tris{(N‐tert‐butyl)(3,5‐dimethylanilido)titanium(III) and the useful tantalum(IV) complex TaCl4(tmeda). The chapter is completed by the synthesis of 1,3,5‐tri‐tert‐butylcyclopentadiene and its sodium and magnesium salts and of a series of tetraalkylammonium salts of tetrafluoroborate and fluoroarylborate salts.

The editor thanks the many (>140!) authors and checkers who contributed to this volume for their hard work and patience. In addition, many other people have helped to bring this volume to completion. Not the least among these are the editor’s undergraduate and graduate coworkers, who contributed greatly to expediting the submission and checking of various syntheses. In addition, the editor gratefully acknowledges the huge contribution of his assistant William Angel for maintaining the organization of the volume as well as the performance of numerous tasks associated with bringing the preparations to a state where they could be submitted to the printer. The editor also thanks Tom Rauchfuss, Greg Girolami, and Al Sattelberger for frequent advice and encouragement.

PHILIP P. POWER

University of California at Davis