REAGENTS FOR TRANSITION METAL COMPLEX AND ORGANOMETALLIC SYNTHESES：INORGANIC SYNTHESES VOLUME TWENTY EIGHT

The volumes in this continuing series provide a compilation of current techniques and ideas in inorganic synthetic chemistry. Includes inorganic polymer syntheses and preparation of important inorganic solids, syntheses used in the development of pharmacologically active inorganic compounds, small-molecule coordination complexes, and related compounds. Also contains valuable information on transition organometallic compounds including species with metal-metal cluster molecules. All syntheses presented here have been tested.

Chapter One COMPLEXES WITH WEAKLY COORDINATED LIGANDS.

1. Metal Complexes with Weakly Bonded Anions: General Considerations.

2. Carbonyl(η⁵-cyclopentadienyl) (tetrafluoroborato)molybdenum and -tungsten complexes: CpM(CO)₂(L) (BF₄) (M = Mo, W; L = CO, PPh₃).

3. Pentacarbonyl(tetrafluoroborato)rhenium and -manganese and Reactions Thereof: M(CO)₅(BF₄) (M = Mn, Re).

4. Iridium(III) Complexes with the Weakly Bonded Anions [BF^-₄] and [OSO₂CF^-₃].

5. cis-Chlorobis(triethylphosphine) (trifluoromethanesulnato)-platinum(II).

6. Tricarbonyltris(nitri1e) Complexes of Cr, Mo, and W: M(CO)₃(NCEt)₃ (M = Cr, Mo, W).

7. The Synthesis of Molybdenum and Tungsten Dinitrogen Complexes: MoCl₄(L)₂, MoCl₃(L)₃ (L = NCMe, THF), Mo(N₂)₂ (dppe)₂, W(N₂)₂(dppe)₂.

8. trans-Bis[ 1,2-ethanediylbis (diphenylphosphine)] bis-(isocyanomethane)tungsten(0): trans-[W(CNR)₂(Ph₂PCH₂CH₂PPh₂)₂].

9. Tricarbonyl(cycloheptatriene) molybdenum(0): Mo(CO)₃(C₇H₈).

10. Tetracarbonyl(η²-Methyl Acry1ate)Ruthenium: Ru(CO)₄(η²-CH₂ =C(H)(CO₂Me)).

11. Reagents for the Synthesis of η-Diene Complexes of Tricarbonyliron and Tricarbonylruthenium.

12. Dihydridobis(solvent) bis(triphenylphosphine) iridium(III) Tetrafluoroborates: Ir(COD)(PPh₃)⁺₂, Ir(H)₂(PPh₃)₂(L)⁺₂ (L = acetone, H₂O).

13. Bis(benzonitrile)dichloro Complexes of Palladium and Platinum: MCl₂(NCPh)₂ (M = Pd, Pt).

14. Acetonitrile Complexes of Selected Transition Metal Cations: Pd(NCMe)²⁺₄, M(NO)₂(NCMe)²⁺₄ (M = Mo, W).

15. Tetrakis(acetonitrile)copper(l +) Hexafluorophosphate(1-): [Cu(NCMe)₄]⁺.

16. Trifluoromethanesulfonates and Trifluoromethanesulfonato-O Complexes.

Chapter Two LOW-VALENT COMPLEXES OF Rh, Ir, Ni, Pd, and Pt.

17. Chlorotris(triphenylphosphine)rhodium(I) (Wilkinson's Catalyst): Rh(Cl)(PPh₃)₃.

18. trans-Carbonylchlorobis (triphenylphosphine)rhodium and Related Complexes: Rh(Cl)(CO)(PPh₃)₂.

19. Hydrido Phosphine Complexes of Rhodium(I): Rh(H)(PPh₃)₄, Rh(H)(CO)(PPh₃)₃.

20. Tetracarbonyldichlorodirhodium: [Rh(Cl)(CO)₂]₂.

21. Di-μ-chlorotetrakis(ethene) dirhodium(I): [Rh(Cl)(C₂H₄)₂]₂.

22. Di-μ-chloro-bis(η⁴-1,5-cyclooctadiene) dirhodium(I): [Rh(Cl)(COD)]₂.

23. Chlorobis(cyclooctene)rhodium(I) and -iridium(I) Complexes: [M(Cl)(C₈H₁₄)₂]₂ (M = Rh, Ir).

24. trans-Carbonylchlorobis (triphenylphosphine) iridium: Ir(Cl)(CO)(PPh₃)₂.

25. Bis(1, 5-cyclooctadiene)nickel(0): Ni(COD)₂.

26. Complexes of Nickel(0): Ni(CN-t-Bu)₄, Ni(PPh₃)₄.

27. Tetrakis(triethyl phosphite) nickel(0), palladium(0), and platinum(0) Complexes: M[P(OEt)₃]₄.

28. Tetrakis(triphenylphosphine) palladium(0): Pd(PPh₃)₄.

29. Tetrakis(tert-butyl isocyanide)di-μ-chlorodipalladium(1): Pd(dba)₂, Pd₂Cl₂(CN-t-Bu)₄.

30. Two-Coordinate Phosphine Complexes of Palladium(0) and Platinum(0): M(PR₃)₂(M = Pd, Pt).

31. Three-Coordinate Phosphine Complexes of Platinum(0): Pt(PR₃)₃.

32. Tetrakis(triethylphosphine) platinum(0): Pt(PEt₃)₄.

33. Tris- and tetrakis(triphenylphosphine) platinum(0): Pt(PPh₃)_3,4.

34. Olefin Complexes of Platinum: Pt(COD)₂, Pt(C₂H₄)₃, Pt(C₂H₄)₂(PR₃).

35. Ethene Complexes of Bis(trialkylphosphine) platinum(0): Pt(C₂H4)(PR₃)₂.

Chapter Three SUBSTITUTED METAL CARBONYL COMPLEXES.

36. (η⁶-Arene) tricarbonylchromium Complexes: Cr(η⁶-Arene)(CO)₃.

37. Zero-Valent Isocyanide Complexes of Chromium, Molybdenum, and Tungsten: M(CO)_x(CNR)_6-x (M = Cr, Mo, W).

38. cis-Bis(diethyldithiocarbamato) dinitrosylmolybdenum, Dibromotetracarbonylmolybdenum(II), and Di- and Tricarbonylbis (diethyldithiocarbamato) molybdenum(II): Mo(Br)₂(CO)₄, Mo(CO)_2,3 [S₂CNEt₂], Mo(NO)₂[S₂CNEt₂]₂.

39. Hexacarbonnylbis (η⁵-cyclopentadienyl) dichrominum, molybdenum, and tungsten and Their Analogs: M₂(η⁵-C₅H₄R)₂(CO)₆ (M = Cr, Mo, and W; R = H, Me, or PhCH₂).

40. Cyclopentadienyl Metal Carbonyl Dimers of Molybdenum and Tungsten: [CpM(CO)₃]₂, [CpM(CO)₂]₂ (M = Mo, W).

41. Pentacarbonylmanganese Halides: Mn(CO)₅X (X = Cl, Br, I).

42. Pentacarbonylrhenium Halides: Re(CO)₅X (X = C1, Br, I).

43. Pentacarbonylhydridorhenium: Re(CO)₅H.

44. Tetracarbonyliron(0) Complexes Containing Group V Donor Ligands: Fe(CO)₄(PR₃).

45. Bis(phosphine) Derivatives of Iron Pentacarbonyl and Tetracarbonyl (tri-tert-butylphosphine)iron(0): Fe(CO)₃(PR₃)₂.

46. Zero-Valent Iron Isocyanide Complexes: Fe(CO)_x(CNR)_5-x.

47. Dicarbonyl(η⁵-cyclopentadienyl) (thiocarbonyl)iron(1+) Trifluoromethanesulfonate (1 - ) and Dicarbonyl(η⁵-

cyclopentadienyl) [methylthio)thiocarbonyl]iron: CpFe(CO)₂(CS)⁺, CpFe(CO)₂ [C( =S)SMe].

48. Tetracarbonylbis(η⁵-cyclopentadienyl) diruthenium: [CpRu(CO)₂]₂.

Chapter Four METAL CARBONYL ANION COMPLEXES.

49. Sodium Hexacarbonylniobate(1 - ): Nb(CO)^-₆.

50. Dicarbonyl(η⁵-cyclopentadieny1) nitrosyl Complexes of Chromium, Molybdenum, and Tungsten: CpM(CO)^-₃, CpM(CO)₂(NO) (M = Cr, Mo, W).

51. Acetylpentacarbonylmanganese and Acetylpentacarbonylrhenium: M(CO)^-₅, M(CO)₅[C(=O)Me] (M = Mn, Re).

52. Sodium Carbonyl Ferrates, Na₂[Fe(CO)₄], Na₂[Fe₂(CO)₈], and Na₂[Fe₃(CO)₁₁], Bis[μ-nitrido-bis(triphenylphosphorus) (l + )] Undecacarbonyltriferrate(2 - ), [(Ph₃P)₂N]₂[Fe₃(CO)₁₁].

53. Dicarbonyl(η⁵-cyclopentadienyl) (2-methyl-l-propenyl-kC¹)iron and Dicarbonyl(η⁵-cyclopentadienyl)(η²-2-methyl-l-propene)iron(l + ) Tetrafluoroborate(1 - ): CpFe(CO)^-₂, CpFe(CO)₂[CH₂=CMe₂]⁺.

54. μ-Nitrido-bis(triphenylphosphorus)1( + ) Tetracarbonylrhodate(1 - ) and μ-Nitrido-bis(triphenylphosphorus) (1 + ) Tetracarbonyliridate(1 - ): [(Ph3P)2N] [M(CO)4] (M = Rh, Ir).

Chapter Five METAL CLUSTER COMPLEXES.

55. Polynuclear Ruthenium Complexes: Ru₃(CO)₁₂, H₄Ru₄(CO)₁₂.

56. Tri- and Tetranuclear Carbonyl-Ruthenium Clusters Containing Isocyanide, Tertiary Phosphine and Phosphite Ligands. Radical Ion-Initiated Substitution of Metal Cluster Carbonyl Complexes Under Mild Conditions: Ru₃(CO)_12-x(L)_x, H₄Ru₄(CO)_12-x(L)_x.

57. Dodecacarbonyltriosmium: OS₃(CO)₁₂.

58. Some Useful Derivatives of Dodecacarbonyltriosmium: Os₃(CO)₁₁(NCMe), Os₃(CO)₁₀(NCMe)₂.

59. μ-Nitrido-bis(triphenylphosphorus) ( 1 + )μ-carbonyl- decacarbonyl-μ-hydridotriosmate(1 - ): HOs₃(CO)^-₁₁.

60. Decacarbonyldi-μ-hydridotriosmium: Os₃(μ-H)₂(CO)₁₀.

61. Dodecacarbonyltetra-μ-hydrido-tetrahedro-tetraosmium: H₄Os₄(CO)₁₂.

62. Tri-μ-carbonyl-nonacarbonyltetrarhodium: Rh₄(CO)₁₂.

63. Dodecacarbonyltetrairidium: Ir₄(CO)₁₂.

Chapter Six CYCLOPENTADIENYL COMPLEXES.

64. Dicarbonylbis(η⁵-cyclopentadienyl) Complexes of Titanium, Zirconium, and Hafnium: Cp'₂M(CO)₂ (Cp' = C₅H₅, C₅Me₅; M = Ti, Zr, Hf).

65. (η⁵-Cyclopentadienyl) hydridozirconium Complexes: Cp₂ZrH₂, Cp₂Zr(H)(Cl).

66. Cyclopentadienyl Complexes of Titanium(III) and Vanadium(III): Cp₂MCl (M = Ti, V).

67. Vanadocene, Bis(η5-cyclopentadienyl)vanadium: Cp₂V, V2(μ-Cl)₃(THF)²⁺₆.

68. Dichlorobis(η⁵-cyclopentadienyi)niobium(IV): Cp₂NbCl₂.

69. Chloro(η⁵-cyclopentadienyl) bis(triphenylphosphine) -ruthenium(II): RuCl(PPh₃)₂(η⁵-C₅H₅).

70. (η⁵-Pentamethy1cyclopentadienyl) cobalt Complexes: Cp*Co(CO)₂, Cp*Co(C₂H₄)₂.

71. Cyclopentadienylbis (trimethy1phosphine) and Cyclopentadienylbis (trimethy1phosphite) Complexes of Co and Rh: CpM(PMe₃)₂, CpM[P(OMe)₃]₂, (M = Co, Rh).

Chapter Seven LANTHANIDE AND ACTINIDE COMPLEXES.

72. Lanthanide Trichlorides by Reaction of Lanthanide Metals with Mercury(II) Chloride in Tetrahydrofuran: LnCl₃(THF)x.

73. (η⁵-Cyclopentadienyl)lanthanide Complexes from the Metallic Elements: Cp₃Ln (Ln = Nd, Sm), Cp₂,Y(DME).

74. Bis(η⁵-pentamethylcyclopentadienyl) bis(tetrahydrofuran)-samarium(II): Cp^*₂Sm(THF)2.

75. Chlorotris(η⁵-cyclopentadienyl) Complexes of Uranium(IV) and Thorium(IV): Cp₃MCl (M = U, Th).

Chapter Eight LIGANDS AND OTHER TRANSITION METAL COMPLEXES.

76. Trimethylphosphine: PMe₃.

77. Phosphorus Trifluoride: PF₃.

78. Cyclopentadienylthallium: CpTl.

79. 1,2,3,4,5-Pentamethylcyclopentadiene: C₅Me₅H.

80. Anhydrous Metal Chlorides.

81. Tungsten and Molybdenum Tetrachloride Oxides: MOCl₄ (M = Mo, W).

82. Tungsten Chloro Phosphine Complexes: WCl₄(PR₃)_2,3, WCl₂(PR₃)₄.

83. Tetrabutylammonium Octachlorodirhenate(III): Re₂Cl^2-₈.

84. Di-μ-chloro-bis[ tricarbonylchlororuthenium(II)]: [Ru(CO)₃Cl₂]₂.

85. Dihydridotetrakis (triphenylphosphine) ruthenium(II): H₂Ru(PPh₃)₄.

86. Tris(2,2'-bipyridine)ruthenium(II) Dichloride Hexahydrate: Ru(bipy)²⁺₃.

87. Dichlorobis[μ-methylenebis (diphenylphosphine)]-dipalladium(I) (Pd-Pd): Pd₂(dppm)₂Cl₂.

88. (η³-Allyl)palladium(II) Complexes: (η³-C₃H₅)₂Pd₂Cl₂, (η³-C₃H₅) (η⁵-C₅H₅)Pd.

89. Cyclic Diolefin Complexes of Platinum and Palladium: MCl₂(COD) (M = Pd, Pt).

90. Potassium Trichloro(ethene) platinate(II) (Zeise's Salt): K[PtCl₃(C₂H₄)].

Index of Contributors.

Subject Index.

Formula Index.