I have a number of boards. Dual socket 7, socket 8, socket 370, PII and one dual PIII Xeon board from Asus. There's also an HP Kayak machine buried somewhere that hangs after POST. Still need to look into that.
Actually, right now I'm working on that dual Socket 8 machine. It needs a new CMOS battery but it's just about ready to take an install....
I ran a dual socket 8 system with Win2k for my kids for a while. I took some leftover server parts and a tower case and a Win2k COA with CD and built it up for them. 256MB of RAM, dual 200MHz 1MB cache, small five-drive RAID of 4GB SCSI drives (full-height 5.25 inch Seagates......). It made quite the racket spinning up. It was just fast enough for what they wanted to do, which involved some games on CD, an interactive CD that came with one of my daughters' dolls, and basic web browsing. It lasted a couple of years, and when it died (voltage regulator failure; failed in an overvoltage mode that fried the rather expensive 1MB cache CPUs and chipset....) I gave them my old Sony Viao Athlon XP 1.2GHz with 512MB RAM (which has since died); it was quite a bit faster than the old dual 200 PPro.
I currently have several multi-processor systems; the question was about motherboards, though, but I guess the DEC AlphaServer 2100's mainboard qualifies, even though the CPU modules are slotted (Pentium II was slotted, too, though), and it has four 275MHZ CPUs and 1GB of RAM. I also have a SPARCStation 10 and a SPARCstation 20, but I only have one working CPU module in each of those due to overheating with duals. I had four Sun Enterprise 450's, and those had quad 400MHz UltraSPARC's in them; still have an Ultra 60 with dual CPU's and an Enterprise 6500 with 18 CPUs. (although the E6500 doesn't have a 'motherboard' in the ordinary sense, rather it has a centerplane that carries the 512 bit bus between CPU/RAM modules and I/O modules). Also have an Ultra 2 somewhere. And while I won't count the 30 CPU Altix 350 system (even though each node has two CPU's mounted to what could loosely be called a motherboard) I will count the Altix 3700 with 4 CPU's, as it does have a multi-cpu motherboard, it is Intel-based (Itanium, maybe, but still Intel!), and has PCI slots (although those are in an 'expansion chassis,' aka IX-Brick).
There's a PowerMac G4 FW800 (the MDD's successor) with dual 1.42GHz CPU's under my desk at work, although the motherboard itself only has a single socket, with the CPU daughterboard having two CPU chips soldered on. And I'm waiting for a couple of Dell PowerEdge 6950's to come available, each with four dual core Opteron 2.8GHz CPU's and 32GB of RAM...... I've always wanted a quad-socket system at home to help with the heating in winter. I would just need to find a x1 or x4 PCIe graphics card to make it a reasonable workstation. Heh, didn't either CPU magazine or MaximumPC a few years back feature a quad-socket system as a workstation; had 24 cores in those four sockets as I recall?
I had an HP server at one time with dual Pentium 133's, and ran Linux on it, but the motherboard died and it went to the recycler.
But my earliest true multiprocessor system I no longer have, unfortunately. It wasn't exactly a multi-processor motherboard, but it did have two CPU cards in the card cage connected to a backplane. Not SMP, either, as one CPU was Z80 and the other was 68K; I am of course talking of a TRS-80 Model II upgraded to a 16, running TRS-Xenix.
Likewise, if you want to be technical, a Commodore VIC-20 or 64 with a 1540 or 1541 disk drive was multiprocessor (two 6502 'cores') but it wasn't a motherboard-based system. The Commodore 128 on the other hand.....
And I have a half-dozen or more dual slot-1 boards, one of which is a 440FX-based board that can take a Socket 8 to slot 1 slotket board and PPro CPU packages (440FX was last chipset to officially support PPro).
As far as OS, I can confirm that WIndows NT 4.0 for sure supported SMP systems. I'm not sure about 3.51, as I never actually ran any of that. Linux SMP support dates from the 2.0 kernel, released in June 1996. So we're actually coming up on the 20th anniversary of stable Linux SMP support...... heh, my old Red Hat Linux 4.x CD set I purchased will soon actually be vintage.....