Comprehensive Coordination Chemistry II: From Biology to by Jon A. MacCleverty, Thomas J. Meyer, E. C. Constable, J. R.

By Jon A. MacCleverty, Thomas J. Meyer, E. C. Constable, J. R. Dilworth

This quantity provides a survey of important advancements within the chemistry of teams 7 and eight ofthe transition metals because the book of finished Coordination Chemistry (CCC) in 1987. the fabric for every point is geared up by means of oxidation kingdom of the steel and in addition by way of thenature of the ligands concerned, with extra sections overlaying particular good points of the coordinationchemistry and purposes of the complexes.

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85 A˚) both of which contain exclusively triply bridging oxo groups. Reaction of the Mn4O46þ cubane core complex Mn4O4L6 (L = diphenylphosphinate, Ph2PO2À) with a hydrogen atom donor, phenothiazine (pzH), has been shown to form the dehydrated cluster Ph Ph P Ph Ph O P O O O Mn O Ph Mn O O O Ph P O P Mn Ph O O O O Ph Ph O Mn O P O P Ph O O Ph Ph Ph O Mn O MnIV Mn O O O O Ph O Mn O O Ph O O O O O Mn O Mn O Mn O O Mn IV O O Ph X Mn O Mn O O Mn O O O Mn IV O O O Figure 10 Cubane complexes with bridging phosphinato and carboxylato ligands.

7 V vs. SCE. Mn R O R O R O Mn O R R = alkyl or aryl group Mn O O Mn O O O O OO O Mn Mn O triangular a O O O O O Mn Mn O O triangular c O triangular b N Mn O O O O N Mn O N O O Mn N Mn O N N O triangular d Figure 21 Core types observed for trinuclear manganese(III) complexes. 47 Manganese Table 7 Electronic spectral properties for dinuclear manganese(III)–carboxylato complexes. Compound Solvent (", MÀ1 cmÀ1), nm References (TMA)3[Mn2(Lc)4(HLc)]ÁH2O [Mn2(BSP)(OCH3)(OAc)(MeOH)2] (Br) ? 5H2O CH3CN [Mn2O(OAc)2(TMIP)2](ClO4)2 CH3CN [Mn2O(OAc)2(TMIP)2](PF6)2 CH3CN 410(730) 373(2,910), 427 sh(651), 610(137) 373(2,880), 420 sh(650), 610(135) 373(2,950), 430 sh(616), 611(143) 370(2,870), 430 sh(624), 612(136) 373(3,070), 433 sh(600), 611(141) 496(405), 523(305), 733(308) 260, 295, 380 sh, 490(225), 532(242) 495(524), 527(418), 711(176) 240(5,800), 295(5,670), 385(300), 490(146), 640(108) 280(17,000), 416 sh(492) 492(361), 556(246) 283(7,000), 468 sh(275) 280(15,000), 340 sh(740), 502 sh(135) 283(6,000), 385 sh(405), 458 sh(165), 486(210), 503 sh (190), 524 sh(175), 540 sh(165), 582 sh(95), 760(58) 232(3,400), 280(3,800), 495(324), 520(250), 545 sh, 560 sh, 570 sh, 665(95), 910(40) 250 sh, 300(14,000), 486(667), 521(638), 720(104), 1,000(63) 246(11,000), 304(12,000), 481(770), 521(740), 680 sh(200) 377 sh, 487(517), 521(372), 545 sh, 569 sh, 728(112) 255(23,900), 376(844), 464(330), 484(405), 497(383), 521 sh(349), 568 sh(216), 736(106) 249(24,900), 372 sh(840), 464 sh(360), 485(460), 502(430), 521 sh(400), 568 sh(240), 757(130) 253 253 253 253 257 258 259 263 267 267 267 267 261 260 260 269 272 270 270 The difference between the planar tetranuclear complexes with a [Mn4O2(OAc)6]2þ core and the butterfly tetranuclear complexes with a [Mn4O2(OAc)7]þ core is due to the seventh bridging carboxylate in the latter.

201 The results have shown that the identity of the bridging ligand, XÀ, has minimal influence on the resultant structures, magnetic properties, 1H NMR and EPR spectral properties, or the redox behavior. All the complexes display a spin ground state of S = 9/2. 233 The crystal structure shows that two [Mn4O3Cl]6þ cubane units are bridged by a nearly linear [Mn3O4]þ unit to give the [MnIII9MnIV2]35þ core. The manganese centers in each cubane unit that are ligated to bpy ligand are in the þ4 state.

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