Molybdenum and Tungsten Structural Differences are Dependent on ndz2/(n + 1)ѕ Mixing: Comparisons of (silox)3MX/R (M = Mo, W; silox = tBu3SiO)

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Article discussing molybdenum and tungsten structural differences being dependent on ndz2/(n + 1)s mixing and a comparison of (silox)3MX/R (M = Mo, W; silox - tBu3SiO).

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Kuiper, David S.; Douthwalte, Richard E.; Mayoi, Ana-Rita; Wolczanski, Peter T.; Lobkovsky, Emil B.; Cundari, Thomas R., 1964- et al. July 15, 2008.

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Article discussing molybdenum and tungsten structural differences being dependent on ndz2/(n + 1)s mixing and a comparison of (silox)3MX/R (M = Mo, W; silox - tBu3SiO).

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15 p.

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Reprinted with permission from Inorganic Chemistry. Copyright 2008 American Chemical Society.

Abstract: Treatment of trans-(Et2O)2MoCI4 with 2 or 3 equiv of Na(silox) (i.e., NaOSitBu3) afforded (silox)3MoCI2 (1-Mo) or (silox)3MoCI (2-Mo). Purification of 2-Mo was accomplished via addition of PMe3 to precipitate (silox)3CIMoPMe3 (2-MoPMe3), followed by thermolysis to remove phosphine. Use of MoCI3(THF)3 with various amounts of Na(silox) produced (silox)2CIMoMoCI(silox)2 (3-Mo). Alkylation of 2-Mo with MeMgBr or EtMgBr afforded (silox)3MoH, which was prepared from 2-Mo and NaBEt3H. Thermolysis of WCI6 with HOSitBu3 afforded (silox)2WCI4 (4-W), and sequential treatment of 4-W with Na/Hg and Na(silox) provided (silox)3WCI2 (1-W, tbp, X-ray), which was alternatively prepared from trans-(Et2S)2WCI4 and 3 equiv of TI(silox). Na/Hg reduction of 1-W generated (silox)3WCI (2-W). Alkylation of 2-W with MeMgBr produced (silox)3WMe (2-WMe), which dehydrogenated to (silox)3WCH (6-W) with ∆ H‡ = 14.9(9) kcal/mol and ∆S‡ = -26(2) eu. Magnetism and structural studies revealed that 2-Mo and 2-MoEt have triplet ground states (GS) and distorted trigonal monopyramid (tmp) and tmp structures, respectively. In contrast, 2-W and 2-WMe possess squashed-Td (distorted square planar) structures, and the former has a singlet GS. Quantum mechanics/ molecular mechanics studies of the S = 0 and S = 1 states are full models of 2-Mo, 2-MoEt, 2-W, and 2WMe corroborate the experimental findings and are consistent with the greater ndz2I(n + 1)s mixing in the third-row transition-metal species being the dominant feature in determining the structural disparity between molybdenum and tungsten.

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  • Inorganic Chemistry, 47(16), American Chemical Society, July 15, 2008, pp. 1-15

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  • Publication Title: Inorganic Chemistry
  • Volume: 47
  • Issue: 16
  • Page Start: 7139
  • Page End: 7153
  • Peer Reviewed: Yes

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  • July 15, 2008

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Kuiper, David S.; Douthwalte, Richard E.; Mayoi, Ana-Rita; Wolczanski, Peter T.; Lobkovsky, Emil B.; Cundari, Thomas R., 1964- et al. Molybdenum and Tungsten Structural Differences are Dependent on ndz2/(n + 1)ѕ Mixing: Comparisons of (silox)3MX/R (M = Mo, W; silox = tBu3SiO), article, July 15, 2008; [Washington, DC]. (https://digital.library.unt.edu/ark:/67531/metadc77130/: accessed July 18, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT College of Arts and Sciences.

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