From owner-chemistry*- at -*ccl.net Thu Sep 25 08:03:00 2014 From: "Sergio Manzetti sergio.manzetti[*]outlook.com" To: CCL Subject: CCL: Metal-Carbene sigma type bond Message-Id: <-50531-140925031318-17222-0fMgbiUSV1P1T7eAcYisjw-x-server.ccl.net> X-Original-From: "Sergio Manzetti" Date: Thu, 25 Sep 2014 03:13:16 -0400 Sent to CCL by: "Sergio Manzetti" [sergio.manzetti/./outlook.com] Dear Tom. You mention the difference between the d-orbitals versus the p atomic orbital which makes the difference. Is this simple the HOMO-LUMO gap in few words, or would it be more intricate, such as the difference between occupied and non-occupied AOs of both the metal and the carbon. I Had the impression from one of the books that the antibonding orbital (2py empty) of the carbon forms a pi bond with an occupied d sub-orbital, assuming dxy (I cannot remember which). Nevertheless, this interaction is completely gone in the Schrock mechanism, and it seems that the Schrock is dependent on triplet states, which in turn depend on the nuclear properties, thus the atom. However, I am still not clear on where the threshold goes between Fischer and Schrock types, and you mention correctly that there is a continuum with two extremes on each side. Would this mean that the Lantanides are more Schrock types, while the 4th row metals are Fischer types? I haven't read you book yet, I will get there soon. Best wishes Sergio Dear Sergio - There are many ways that have been used to describe transition metal - carbene bonding. The bottom line is whether or not one gets anymore physical insight to "real" molecules. You are not correct in stating that Schrock-type complexes are more likely for heavier transition metals. Foe example, there are many Pd or W complexes which are the Fisher type, i.e. have carbene carbons that are electrophilic in nature. I would prefer to view these two types as opposites on a continuum where it is the energetic difference in the metal d orbitals versus the carbene p AO forming the pi bond which makes the difference. This is all spelled out fairly clearly (I think) in the Albright, Burdett, Whangbo "Orbital Interactions in Chemistry" 2nd Ed.book - complete with plots of the MOs. I am on vacation so I can't give you the page numbers. On Sep 18, 2014, at 9:41 AM, Sergio Manzetti sergio.manzetti%%outlook.com wrote: Sent to CCL by: "Sergio Manzetti" [sergio.manzetti-.-outlook.com] Dear Fedor, thanks. I have looked further in the book, and it seems there are two mechanisms at hand: one Fischer mechanism and one other the Schrock mechanism. The difference between the two, is that one considers the Metal bonding d-electrons as a singlet, while the other as a triplet. The singlet gives apparently a "regular" double bond by 4 electrons, pairing with the carbons 2p2. While the other, has one electron in the dxy and the other in the dxz, each of these unpaired electrons form a pair with the unpaired electrons of equally considered carbene in its triplet state. Eventually, it says that the latter (The Schrock mechanism) is more for likely for the heavier transition metals, while the Fischer more likely for light metals, such as Cr and V. Your guess on the non-participating 6s2 was right. I take its because the 6s really has a slightly lower energy than the 5d, at the end of the day (aufbau). Thanks for your tip. I May use software to check it out. Sergio From: owner-chemistry .. ccl.net To: sergio.manzetti .. gmx.com Subject: CCL: Metal-Carbene sigma type bond Date: Thu, 18 Sep 2014 13:46:58 +0200 Sent to CCL by: Fedor Goumans [goumans^-^scm.com] Hi Sergio, You may consider using any of the chemical bonding analysis tools out there to dig in to the bonding situation (aside from the phenomenological Dewar-Chatt-Duncanson model). Or if anything, just look at the Mulliken population analysis. My guess is that for tantalum carbene complexes the 6s orbitals will not be occupied at all. I suggest the thorough paper by Frenking et al. (Chemical bonding in transition metal carbene complexes, J. Organomet. Chem. 690, p. 6178-6204 (2005)) as a starting point. Most of it is on Cr carbenes, but you can exctend the analysis to group-5 transition metals as well ('early TMs'). Best wishes, Fedor On 9/18/2014 10:44 AM, Sergio Manzetti sergio.manzetti a outlook.com wrote: Sent to CCL by: "Sergio Manzetti" [sergio.manzetti!=!outlook.com] Dear all, I have a question regarding the formation of a sigma-type bond between Tantalum and the carbene ion. The sigma type bond is apparently a sp2 hybridized bond. Accounting for the configuration of carbon, it donates its two 2px electrons which interact with one of the tantalum 6s? The pi type bond is more clear, it is formed by an empty 2py of the carbon interacting with one of the 5d electrons. However, if the sigma type bond is formed by two 2px electrons, where does the second 6s electron go? Alternatively, this was wrong assumption. Orginally, I was looking for the energy diagram of the sigma type bond of the Ta=CH2, but could not find it. Thanks> -- Dr. T. P. M. (Fedor) Goumans Business Developer Scientific Computing & Modelling NV (SCM) Vrije Universiteit, FEW, Theoretical Chemistry De Boelelaan 1083 1081 HV Amsterdam, The Netherlands T +31 20 598 7625 F +31 20 598 7629 E-mail: goumans**scm.com http://www.scm.comthe strange characters on the top line to the ,, sign. You can alsoE-mail to subscribers: CHEMISTRY,,ccl.net or use:E-mail to administrators: CHEMISTRY-REQUEST,,ccl.net or use from CCL with 5.7.1 error, check:With Best Regards Tom Albright Too many newsletters? You can unsubscribe.